The invention concerns novel homo- and copolymers of ethylene and/or one or more acyclic olefins, and/or selected cyclic olefins, and optionally selected ester, carboxylic acid, or other functional group containing olefins as comonomers; selected transition metal containing polymerization catalysts; and processes for making such polymers, intermediates for such catalysts, and new processes for making such catalysts. Also disclosed herein is a process for the production of linear alpha-olefins by contacting ethylene with a nickel compound of the formula [DAB]NiX2 wherein DAB is a selected xcex1-diimine and X is chlorine, bromine, iodine or alkyl, and a selected Lewis or Bronsted acid, or by contacting ethylene with other selected xcex1-diimine nickel complexes
Homo- and copolymers of ethylene (E) and/or one or more acyclic olefins, and/or cyclic olefins, and/or substituted olefins, and optionally selected olefinic esters or carboxylic acids, and other types of monomers, are useful materials, being used as plastics for packaging materials, molded items, films, etc., and as elastomers for molded goods, belts of various types, in tires, adhesives, and for other uses. It is well known in the art that the structure of these various polymers, and hence their properties and uses, are highly dependent on the catalyst and specific conditions used during their synthesis. In addition to these factors, processes in which these types of polymers can be made at reduced cost are also important. Therefore, improved processes for making such (new) polymers are of interest. Also disclosed herein are uses for the novel polymers.
xcex1-Olefins are commercial materials being particularly useful as monomers and as chemical intermediates. For a review of xcex1-olefins, including their uses and preparation, see B. Elvers, et al., Ed., Ullmann""s Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A13, VCH Verlagsgesellschaft mbH, Weinheim, 1989, p. 238-251. They are useful as chemical intermediates and they are often made by the oligomerization of ethylene using various types of catalysts. Therefore catalysts which are capable or forming xcex1-olefins from ethylene are constantly sought.
This invention concerns a polyolefin, which contains about 80 to about 150 branches per 1000 methylene groups, and which contains for every 100 branches that are methyl, about 30 to about 90 ethyl branches, about 4 to about 20 propyl branches, about 15 to about 50 butyl branches, about 3 to about 15 amyl branches, and about 30 to about 140 hexyl or longer branches.
This invention also concerns a polyolefin which contains about 20 to about 150 branches per 1000 methylene groups, and which contains for every 100 branches that are methyl, about 4 to about 20 ethyl branches, about 1 to about 12 propyl branches, about 1 to about 12 butyl branches, about 1 to about 10 amyl branches, and 0 to about 20 hexyl or longer branches.
Disclosed herein is a polymer, consisting essentially of repeat units derived from the monomers, ethylene and a compound of the formula CH2xe2x95x90CH(CH2)mCO2R1, wherein R1 is hydrogen, hydrocarbyl or substituted hydrocarbyl, and m is 0 or an integer from 1 to 16, and which contains about 0.01 to about 40 mole percent of repeat units derived from said compound, and provided that said repeat units derived from said compound are in branches of the formula xe2x80x94CH(CH2)nCO2R1, in about 30 to about 70 mole percent of said branches n is 5 or more, in about 0 to about 20 mole percent n is 4, in about 3 to 60 mole percent n is 1, 2 and 3, and in about 1 to about 60 mole percent n is 0.
This invention concerns a polymer of one or more alpha-olefins of the formula CH2xe2x95x90CH(CH2)aH wherein a is an integer of 2 or more, which contains the structure (XXV) 
wherein R35 is an alkyl group and R36 is an alkyl group containing two or more carbon atoms, and provided that R35 is methyl in about 2 mole percent or more of the total amount of (XXV) in said polymer.
This invention also includes a polymer of one or more alpha-olefins of the formula CH2xe2x95x90CH(CH2)aH wherein a is an integer of 2 or more, wherein said polymer contains methyl branches and said methyl branches comprise about 25 to about 75 mole percent of the total branches.
This invention also concerns a polyethylene containing the structure (XXVII) in an amount greater than can be accounted for by end groups, and preferably at least 0.5 or more of such branches per 1000 methylene groups than can be accounted for by end groups. 
This invention also concerns a polypropylene. containing one or both of the structures (XXVIII) and (XXIX) and in the case of (XXIX) in amounts greater than can be accounted for by end groups. Preferably at least 0.5 more of (XXIX) branches per 1000 methylene groups than can be accounted for by end groups, and/or at least 0.5 more of (XXVIII) per 1000 methylene groups are present in the polypropylene. 
Also described herein is an ethylene homopolymer with a density of 0.86 g/ml or less.
Described herein is a process for the polymerization of olefins, comprising, contacting a transition metal complex of a bidentate ligand selected from the group consisting of 
with an olefin wherein:
said olefin is selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, norbornene, or substituted norbornene;
said transition metal is selected from the group consisting of Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd;
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene substituted hydrocarbylene to form a carbocyclic ring;
R44 is hydrocarbyl or substituted hydrocarbyl, and R28 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R44 and R28 taken together form a ring;
R45 is hydrocarbyl or substituted hydrocarbyl, and R29 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R45 and R29 taken together form a ring;
each R30 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R30 taken together form a ring;
R20 and R23 are independently hydrocarbyl or substituted hydrocarbyl;
R21 and R22 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
n is 2 or 3;
R1 is hydrogen, hydrocarbyl or substituted hydrocarbyl;
and provided that:
said transition metal also has bonded to it a ligand that may be displace by said olefin or add to said olefin;
when M is Pd, said bidentate ligand is (VIII), (XXXII) or (XXIII);
when M is Pd a diene is not present; and
when norbornene or substituted norbornene is used no other olefin is present.
Described herein is a process for the copolymerization of an olefin and a fluorinated olefin, comprising, contacting a transition metal complex of a bidentate ligand selected from the group consisting of 
with an olefin, and a fluorinated olefin wherein:
said olefin is selected from the group consisting of ethylene and an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17;
said transition metal is selected from the group consisting of Ni and Pd;
said fluorinated olefin is of the formula H2Cxe2x95x90CH(CH2)aRfR42;
a is an integer of 2 to 20; Rf is perfluoroalkylene optionally containing one or more ether groups;
R42 is fluorine or a functional group;
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene substituted hydrocarbylene to form a carbocyclic ring;
each R17 is independently saturated hydrocarbyl;
and provided that said transition metal also has bonded to it a ligand that may be displaced by said olefin or add to said olefin.
This invention also concerns a copolymer of an olefin of the formula R17CHxe2x95x90CHR17 and a fluorinated olefin of the formula H2Cxe2x95x90CH(CH2)aRfR42, wherein:
each R17 is independently hydrogen or saturated hydrocarbyl;
a is an integer of 2 to 20; Rf is perfluoroalkylene optionally containing one or more ether groups; and
R42 is fluorine or a functional group;
provided that when both of R17 are hydrogen and R42 is fluorine, Rf is xe2x80x94(CF2)bxe2x80x94 wherein b is 2 to 20 or perfluoroalkylene containing at least one ether group.
Described herein is a process for the polymerization of olefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C.:
a first compound W, which is a neutral Lewis acid capable of abstracting either Qxe2x88x92 or Sxe2x88x92 to form WQxe2x88x92 or WSxe2x88x92, provided that the anion formed is a weakly coordinating anion; or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion;
a second compound of the formula 
xe2x80x83and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, or norbornene;
wherein:
M is Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd the m oxidation state;
y+z=m
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or bromide;
S is alkyl, hydride, chloride, iodide, or bromide; and
provided that:
when norbornene or substituted norbornene is present, no other monomer is present;
when M is Pd a diene is not present; and
except when M is Pd, when both Q and S are each independently chloride, bromide or iodide W is capable of transferring a hydride or alkyl group to M.
This invention includes a process for the production of polyolefins, comprising contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C., one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene; with a compound of the formula 
wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94;
n is 2 or 3;
z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6;
X is a weakly coordinating anion;
R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
M is Ni(II) or Pd(II);
each R16 is independently hydrogen or alkyl containing 1 to 10 carbon atoms;
n is 1, 2, or 3;
R8 is hydrocarbyl; and
T2 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R15C(xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94;
and provided that:
when M is Pd a diene is not present; and
when norbornene or substituted norbornene is used no other monomer is present.
This invention includes a process for the production of polyolefins, comprising contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C., one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene; with a compound of the formula 
wherein:
R44 is hydrocarbyl or substituted hydrocarbyl, and R28 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R44 and R28 taken together form a ring;
R45 is hydrocarbyl or substituted hydrocarbyl, and R29 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R45 and R29 taken together form a ring;
each R30 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R30 taken together form a ring;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
R20 and R23 are independently hydrocarbyl or substituted hydrocarbyl;
R21 and R22 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6; and
X is a weakly coordinating anion; and
provided that:
when M is Pd or (XVIII) is used a diene is not present; and
in (XVII) M is not Pd.
This invention includes a process for the production of polyolefins, comprising contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C., one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, 4-vinylcyclohexene, cyclobutene, cyclopentene, substituted norbornene, and norbornene; with a compound of the formula 
wherein:
R20 and R23 are independently hydrocarbyl or substituted hydrocarbyl;
R21 and R22 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C (xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6;
X is a weakly coordinating anion;
R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
M is Ni(II) or Pd(II);
T2 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R15C(xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94;
and provided that:
when M is Pd a diene is not present; and
when norbornene or substituted norbornene is used no other monomer is present.
Described herein is a process for the production for polyolefins, comprising contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C.,
a first compound W, which is a neutral Lewis acid capable of abstracting either Qxe2x88x92 or S to form WQxe2x88x92 or WSxe2x88x92, provided that the anion formed is a weakly coordinating anion; or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion;
a second compound of the formula 
xe2x80x83and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, or norbornene;
wherein:
M is Ti, Zr, V, Cr, a rare earth metal, Co, Fe, Sc, or Ni, of oxidation state m;
R44 is hydrocarbyl or substituted hydrocarbyl, and R28 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R44 and R28 taken together form a ring;
R45 is hydrocarbyl or substituted hydrocarbyl, and R29 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R45 and R29 taken together form a ring;
each R30 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R30 taken together form a ring;
n is 2 or 3;
y and z are positive integers;
y+z=m;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or bromide;
S is alkyl, hydride, chloride, iodide, or bromide; and
provided that;
when norbornene or substituted norbornene is present, no other monomer is present.
Disclosed herein is a process for the production of polyolefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C., one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene; optionally a source of X; with a compound of the formula 
wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene substituted hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that R17 contains no olefinic bonds;
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94;
R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
E is halogen or xe2x80x94OR15;
R18 is hydrocarbyl not containing olefinic or acetylenic bonds; and
X is a weakly coordinating anion;
provided that, when norbornene or substituted norbornene is present, no other monomer is present.
Described herein is a process for the polymerization of olefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C.:
a first compound W, which is a neutral Lewis acid capable of abstracting either Qxe2x88x92 or S to form WQ31  or WSxe2x88x92, provided that the anion formed is a weakly coordinating anion; or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion;
a second compound of the formula 
xe2x80x83and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, 4-vinylcyclohexene, cyclobutene, cyclopentene, substituted norbornene, or norbornene;
wherein:
M is Ni(II), Co(II), Fe(II), or Pd(II);
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or bromide;
S is alkyl, hydride, chloride, iodide, or bromide; and
provided that;
when norbornene or substituted norbornene is present, no other monomer is present;
when M is Pd a diene is not present; and
except when M is Pd, when both Q and S are each independently chloride, bromide or iodide W is capable of transferring a hydride or alkyl group to M.
Included herein is a polymerization process, comprising, contacting a compound of the formula [Pd(R13CN)4]X2 or a combination of Pd[OC(O)R40]2 and HX; a compound of the formula 
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that R17 contains no olefinic bonds;
R13 is hydrocarbyl;
R40 is hydrocarbyl or substituted hydrocarbyl and
X is a weakly coordinating anion;
provided that, when norbornene or substituted norbornene is present, no other monomer is present.
Also described herein is a polymerization process, comprising;
contacting Ni[0], Pd[0] or Ni[I] compound containing a ligand which may be displaced by a ligand of the formula (VIII), (XXX), (XXXII) or (XXIII);
a second compound of the formula 
xe2x80x83an oxidizing agent;
a source of a relatively weakly coordinating anion;
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene;
wherein:
R2 and R are each independently hydrocarbyl or. substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
R13 is hydrocarbyl;
R44 is hydrocarbyl or substituted hydrocarbyl, and R28 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R44 and R28 taken together form a ring;
R45 is hydrocarbyl or substituted hydrocarbyl, and R29 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R45 and R29 taken together form a ring;
each R30 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R30 taken together form a ring;
R46 and R47 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R48 and R49 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl;
R20 and R23 are independently hydrocarbyl or substituted hydrocarbyl;
n is 2 or 3;
R21 and R22 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl; and
X is a weakly coordinating anion;
provided that;
when norbornene or substituted norbornene is present, no other monomer is present;
when said Pd[0] compound is used, a diene is not present; and
when said second compound is (XXX) only an Ni[0] or Ni[I] compound is used.
Described herein is a polymerization process, comprising, contacting an Ni[0] complex containing a ligand or ligands which may be displaced by (VIII), oxygen, an alkyl aluminum compound, and a compound of the formula 
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; and
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
provided that, when norbornene or substituted norbornene is present, no other monomer is present.
A polymerization process, comprising, contacting oxygen and an alkyl aluminum compound, or a compound of the formula HX, and a compound of the formula 
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; and
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
X is a weakly coordinating anion; and
provided that, when norbornene or substituted norbornene is present, no other monomer is present.
Described herein is a polymerization process, comprising, contacting an Ni[0] complex containing a ligand or ligands which may be displaced by (VIII), HX or a Bronsted acidic solid, and a compound of the. formula 
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; and
X is a weakly coordinating anion;
provided that, when norbornene or substituted norbornene is present, no other monomer is present
Described herein is a process for the polymerization of olefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C.:
a first compound W, which is a neutral Lewis acid capable of abstracting either Qxe2x88x92 or Sxe2x88x92 to form WQxe2x88x92 or WSxe2x88x92, provided that the anion formed is a weakly coordinating anion; or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion;
a second compound of the formula 
xe2x80x83and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, or norbornene;
wherein:
M is Ni(II) or Pd(II)
R20 and R23 are independently hydrocarbyl or substituted hydrocarbyl;
R21 and R22 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or bromide;
S is alkyl, hydride, chloride, iodide, or bromide; and
provided that;
when norbornene or substituted norbornene is present, no other monomer is present;
when M is Pd a diene is not present; and
except when M is Pd, when both Q and S are each independently chloride, bromide or iodide W is capable of transferring a hydride or alkyl group to M.
This invention also concerns a process for the polymerization of olefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C., a compound of the formula 
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R27 is independently hydrocarbyl or substituted hydrocarbyl provided that R17 contains no olefinic bonds; and
each R27 is independently hydrocarbyl;
each X is a weakly coordinating anion;
provided that, when norbornene or substituted norbornene is present, no other monomer is present.
This invention also concerns a process for the polymerization of olefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C.:
a first compound W, which is a neutral Lewis acid capable of abstracting either Qxe2x88x92 or Sxe2x88x92 to form WQxe2x88x92 or WSxe2x88x92, provided that the anion formed is a weakly coordinating anion; or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion;
a second compound of the formula 
xe2x80x83and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:
R46 and R47 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R48 and R49 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl;
each R31 is independently hydrocarbyl, substituted hydrocarbyl or hydrogen;
M is Ti, Zr, Co, V, Cr, a rare earth metal, Fe, Sc, Ni, or Pd of oxidation state m;
y and z are positive integers;
y+z=m;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or bromide;
S is alkyl, hydride, chloride, iodide, or bromide; and
provided that;
when norbornene or substituted norbornene is present, no other monomer is present;
when M is Pd a diene is not present; and
except when M is Pd, when both Q and S are each independently chloride, bromide or iodide W is capable of transferring a hydride or alkyl group to M.
Disclosed herein is a compound of the formula 
wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6;
X is a weakly coordinating anion; and
R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
provided that when R3 and R4 taken together are hydrocarbylene to form a carbocyclic ring, Z is not an organic nitrile.
Described herein is a compound of the formula 
wherein:
R50 is substituted phenyl;
R51 is phenyl or substituted phenyl;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
and provided that groups in the 2 and 6 positions of R50 have a difference in Es of about 0.60 or more.
Described herein is a compound of the formula 
wherein:
R52 is substituted phenyl;
R53 is phenyl or substituted phenyl;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
Q is alkyl, hydride, chloride, bromide or iodide;
S is alkyl, hydride, chloride, bromide or iodide;
and provided that;
groups in the 2 and 6 positions of R52 have a difference in Es of 0.15 or more; and
when both Q and S are each independently chloride, bromide or iodide W is capable of transferring a hydride or alkyl group to Ni.
This invention includes a compound of the formula 
wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene, to form a ring;
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94;
R15 is hydrocarbyl not containing an olefinic or acetylenic bond;
Z is a neutral Lewis acid wherein the donating atom is nitrogen, sulfur or oxygen, provided that, if the donating atom is nitrogen, then the pKa of the conjugate acid of that compound is less than about 6; and
X is a weakly coordinating anion.
This invention also concerns a compound of the formula 
wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
M is Ni(II) or Pd(II);
each R16 is independently hydrogen or alkyl containing 1 to 10 carbon atoms;
n is 1, 2, or 3;
X is a weakly coordinating anion; and
R8 is hydrocarbyl.
Also disclosed herein is a compound of the formula 
wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
E is halogen or xe2x80x94OR18;
R18 is hydrocarbyl not containing olefinic or acetylenic bonds;
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94;
R15 is hydrocarbyl not containing olefinic or acetylenic bonds; and
X is a weakly coordinating anion.
Included herein is a compound of the formula [(xcex74-1,5-COD)PdT1Z]+Xxe2x88x92, wherein:
T1 is hydrocarbyl not containing olefinic or acetylenic bonds;
X is a weakly coordinating anion;
COD is 1,5-cyclooctadiene;
Z is R10CN; and
R10 is hydrocarbyl not containing olefinic or acetylenic bonds.
Also included herein is a compound of the formula 
wherein:
M is Ni(II) or Pd(II);
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R11 is independently hydrogen, alkyl or xe2x80x94(CH2)mCO2R1;
T3 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or xe2x80x94CH2CH2CH2CO2R8;
P is a divalent group containing one or more repeat units derived from the polymerization of one or more of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, or norbornene and, when M is Pd(II), optionally one or more of: a compound of the formula CH2xe2x95x90CH(CH2)mCO2R1, CO, or a vinyl ketone;
R8 is hydrocarbyl;
m is 0 or an integer from 1 to 16,
R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;
and X is a weakly coordinating anion;
provided that, when M is Ni(II), R11 is not xe2x80x94CO2R8.
Also described herein is a compound of the formula 
wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
T2 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R15C(xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94;
R15 is hydrocarbyl not containing olefinic or acetylenic bonds; and
X is a weakly coordinating anion.
Included herein is a process for the production of polyolefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C., a compound of the formula 
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene, wherein:
M is Ni(II) or Pd(II);
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R11 is independently hydrogen, alkyl or xe2x80x94(CH2)mCO2R1;
T3 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or xe2x80x94CH2CH2CH2CO2R8;
P is a divalent group containing one or more repeat units derived from the polymerization of one or monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene, and, when M is Pd(II), optionally one or more of: a compound of the formula CH2xe2x95x90CH(CH2)mCO2R1, CO or a vinyl ketone;
R8 is hydrocarbyl;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;
m is 0 or an integer of 1 to 16;
and X is a weakly coordinating anion;
provided that:
when M is Pd a diene is not present;
when norbornene or substituted norbornene is present, no other monomer is present; and
further provided that, when M is Ni(II), R11 is not xe2x80x94CO2R8.
Included herein is a process for the production of polyolefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C., a compound of the formula 
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene, wherein:
M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd of oxidation state m;
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R11 is independently hydrogen, or alkyl, or both of R11 taken together are hydrocarbylene to form a carbocyclic ring;
T3 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or xe2x80x94CH2CH2CH2CO2R8;
P is a divalent group containing one or more repeat units derived from the polymerization of one or monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene, and, when M is Pd(II), optionally one or more of: a compound of the formula CH2xe2x95x90CH(CH2)mCO2R1, CO, or a vinyl ketone;
R8 is hydrocarbyl;
a is 1 or 2;
y+a+1=m;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;
m is 0 or an integer of 1 to 16;
and X is a weakly coordinating anion;
provided that:
when norbornene or substituted norbornene is present, no other monomer is present;
when M is Pd a diene is not present; and
further provided that, when M is Ni(II), R11 is not xe2x80x94CO2R8.
Also described herein is a compound of the formula 
wherein:
M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd of oxidation state m;
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R11 is independently hydrogen, or alkyl, or both of R11 taken together are hydrocarbylene to form a carbocyclic ring;
T3 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or xe2x80x94CH2CH2CH2CO2R8;
P is a divalent group containing one or more repeat units derived from the polymerization of one or monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene, and optionally, when M is Pd(II), one or more of: a compound of the formula CH2xe2x95x90CH (CH2)mCO2R1, CO, or a vinyl ketone;
Q is a monovalent anion;
R8 is hydrocarbyl;
a is 1 or 2;
y+a+=m;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;
m is 0 or an integer of 1 to 16; and
and X is a weakly coordinating anion;
and provided that when M is Pd a diene is not present.
Described herein is a process, comprising, contacting, at a temperature of about xe2x88x9240xc2x0 C. to about +60xc2x0 C., a compound of the formula [(xcex74-1,5-COD)PdT1Z]+Xxe2x88x92 and a diimine of the formula 
to produce a compound of the formula 
wherein:
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94;
X is a weakly coordinating anion;
COD is 1,5-cyclooctadiene;
Z is R10CN;
R10 is hydrocarbyl not containing olefinic or acetylenic bonds;
R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; and
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring.
Described herein is a process, comprising, contacting, at a temperature of about xe2x88x9280xc2x0 C. to about +20xc2x0 C., a compound of the formula (xcex74-1,5-COD)PdMe2 and a diimine of the formula 
to produce compound of the formula 
wherein:
COD is 1,5-cyclooctadiene;
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; and
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring.
Also disclosed herein is a compound of the formula 
wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substitutes hydrocarbylene to form a ring;
each R27 is hydrocarbyl; and
each X is a weakly coordinating anion.
This invention includes a compound of the formula 
wherein:
M is Ni(II) or Pd(II);
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R14 is independently hydrogen, alkyl or xe2x80x94(CH2)mCO2R1;
R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;
T4 is alkyl, xe2x80x94R60C(O)OR8, R15(Cxe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94;
R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
R60 is alkylene not containing olefinic or acetylenic bonds;
R8 is hydrocarbyl;
and X is a weakly coordinating anion;
and provided that when R14 is xe2x80x94(CH2)mCO2R1, or T4 is not alkyl, M is Pd(II).
Describes herein is a homopolypropylene with a glass transition temperature of xe2x88x9230xc2x0 C. or less, and containing at least about 50branches per 1000 methylene groups.
This invention also concerns a homopolymer of cyclopentene having a degree of polymerization of about 30 or more and an end of melting point of about 100xc2x0 C. to about 320xc2x0 C., provided that said homopolymer has less than 5 mole percent of enchained linear olefin containing pentylene units.
In addition, disclosed herein is a homopolymer or copolymer of cyclopentene that has an X-ray powder diffraction pattern that has reflections at approximately 17.3xc2x0, 19.3xc2x0, 24.2xc2x0, and 40.7xc2x0 2xcex8.
Another novel polymer is a homopolymer of cyclopentene wherein at least 90 mole percent of enchained cyclopentylene units are 1,3-cyclopentylene units, and said homopolymer has an average degree of polymerization of 30 more.
Described herein is ahomopolymer of cyclopentene wherein at least 90 mole percent of enchained cyclopentylene units are cis-1,3-cyclopentylene, and said homopolymer has an average degree of polymerization of about 10 or more.
Also described is a copolymer of cyclopentene and ethylene wherein at least 75 mole percent of enchained cyclopentylene units are 1,3-cyclopentylene units.
This invention concerns a copolymer of cyclopentene and ethylene wherein there are at least 20 branches per 1000 methylene carbon atoms.
Described herein is a copolymer of cyclopentene and ethylene wherein at least 50 mole percent of the repeat units are derived from cyclopentene.
Disclosed herein is a copolymer of cyclopentene and an xcex1-olefin.
This invention also concerns a polymerization process, comprising, contacting an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, wherein each R17 is independently hydrogen, hydrocarbyl, or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms with a catalyst, wherein said catalyst:
contains a nickel or palladium atom in a positive oxidation state;
contains a neutral bidentate ligand coordinated to said nickel or palladium atom, and wherein coordination to said nickel or palladium atom is through two nitrogen atoms or a nitrogen atom and a phosphorous atom; and
said neutral bidentate ligand, has an Ethylene Exchange Rate of less than 20,000 L-molxe2x88x921sxe2x88x921 when said catalyst contains a palladium atom, and less than 50,000 L-molxe2x88x921sxe2x88x921 when said catalyst contains a nickel atom;
and provided that when Pd is present a diene is not present.
Described herein is a process for the polymerization of olefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C.:
a first compound which is a salt of an alkali metal cation and a relatively noncoordinating monoanion;
a second compound of the formula 
xe2x80x83and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, or norbornene;
wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that R17 contains no olefinic bond;
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94;
S is chloride, iodide, or bromide; and
provided that, when norbornene or substituted norbornene is present, no_other monomer is present.
Described herein is a polyolefin, comprising, a polymer made by polymerizing one or more monomers of the formula H2Cxe2x95x90CH(CH2)eG by contacting said monomers with a transition metal containing coordination polymerization catalyst, wherein:
each G is independently hydrogen or xe2x80x94CO2R1;
each e is independently 0 or an integer of 1 to 20;
each R1 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
and provided that:
said polymer has at least 50 branches per 1000 methylene groups;
in at least 50 mole percent of said monomers G is hydrogen; and
except when no branches should be theoretically present, the number of branches per 1000 methylene groups is 90% or less than the number of theoretical branches per 1000 methylene groups, or the number of branches per 1000 methylene groups is 110% or more of theoretical branches per 1000 methylene groups, and
when there should be no branches theoretically present, said polyolefin has 50 or more branches per 1000 methylene groups;
and provided that said polyolefin has at least two branches of different lengths containing less than 6 carbon atoms each.
Also described herein is a polyolefin, comprising, a polymer made by polymerizing one or more monomers of the formula H2Cxe2x95x90CH(CH2)eG by contacting said monomers with a transition metal containing coordination polymerization catalyst, wherein:
each G is independently hydrogen or xe2x80x94CO2R1;
each e is independently 0 or an integer of 1 to 20;
R1 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
and provided that:
said polymer has at least 50 branches per 1000 methylene groups;
in at least 50 mole percent of said monomers G is hydrogen;
said polymer has at least 50 branches of the formula xe2x80x94(CH2) fG per 1000 methylene groups, wherein when G is the same as in a monomer and exe2x89xa0f, and/or for any single monomer of the formula H2Cxe2x95x90CH(CH2)eG there are less than 90% of the number of theoretical branches per 1000 methylene groups, or more than 110% of the theoretical branches per 1000 methylene groups of the formula xe2x80x94(CH2)fG and f=e, and wherein f is 0 or an integer of 1 or more;
and provided that said polyolefin has at least two branches of different lengths containing less than 6 carbon atoms.
This invention concerns a process for the formation of linear (xcex1-olefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C.:
ethylene;
a first compound W, which is a neutral Lewis acid capable of abstracting Xxe2x88x92to form WXxe2x88x92, provided that the anion formed is a weakly coordinating anion, or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion; and
a second compound of the formula 
xe2x80x83wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; and
Q and S are each independently chlorine, bromine, iodine or alkyl; and
wherein an xcex1-olefin containing 4 to 40 carbon atoms is produced.
This invention also concerns a process for the formation of linear xcex1-olefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C.:
ethylene and a compound of the formula 
wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
T1 is hydrogen or n-alkyl containing up to 38 carbon atoms;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6;
U is n-alkyl containing up to 38 carbon atoms; and
X is a noncoordinating anion;
and wherein an xcex1-olefin containing 4 to 40 carbon atoms is produced.
Another novel process is a process for the formation of linear xcex1-olefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C.:
ethylene;
and a Ni[II] of 
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene substituted hydrocarbylene to form a carbocyclic ring and
wherein an xcex1-olefin containing 4 to 40 carbon atoms is produced.
Also described herein is a process for the production of polyolefins, comprising, contacting, at a temperature of about 0xc2x0 C. to about +200xc2x0 C., a compound of the formula 
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene, wherein:
M is Ni(II) or Pd(II);
A is a xcfx80-allyl or xcfx80-benzyl group;
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
and X is a weakly coordinating anion;
and provided that:
when M is Pd a diene is not present; and
when norbornene or substituted norbornene is present, no other monomer is present.
The invention also includes a compound of the formula 
wherein:
M is Ni(II) or Pd(II);
A is a xcfx80-allyl or xcfx80-benzyl group;
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
and X is a weakly coordinating anion;
and provided that when M is Pd a diene is not present.
This invention also includes a compound of the formula 
wherein:
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
R54 is hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
each R55 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
W is alkylene or substituted alkylene containing 2 or more carbon atoms;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donatingatom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6, or an olefin of the formula R17CHxe2x95x90CHR17;
each R17 is independently hydrogen, saturated hydrocarbyl or substituted saturated hydrocarbyl; and
X is a weakly coordinating anion;
and provided that when M is Ni, W is alkylene and each R17 is independently hydrogen or saturated hydrocarbyl.
This invention also includes a process for the production of a compound of the formula 
comprising, heating a compound of the formula 
at a temperature of about xe2x88x9230xc2x0 C. to about +100xc2x0 for a sufficient time to produce (XXXVIII), and wherein:
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
R54 is hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
each R55 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R56 is alkyl containing 2 to 30 carbon atoms;
T5 is alkyl;
W is alkylene containing 2 to 30 carbon atoms;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6; and
X is a weakly coordinating anion.
This invention also concerns a process for the polymerization of olefins, comprising, contacting a compound of the formula 
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene, wherein:
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
R54 is hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
each R55 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
W is alkylene or substituted alkylene containing 2 or more carbon atoms;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6, or an olefin of the formula R17CHxe2x95x90CHR17;
each R17 is independently hydrogen, saturated hydrocarbyl or substituted saturated hydrocarbyl; and
X is a weakly coordinating anion;
and provided that:
when M is Ni, W is alkylene and each R17 is independently hydrogen or saturated hydrocarbyl;
and when norbornene or substituted norbornene is present, no other monomer is present.
This invention also concerns a homopolypropylene containing about 10 to about 700 xcex4+ methylene groups per 1000 total methylene groups in said homopolypropylene.
Described herein is a homopolypropylene wherein the ratio of xcex4+:xcex3 methylene groups is about 0.5 to about 7.
Also included herein is a homopolypropylene in which about 30 to about 85 mole percent of the monomer units are enchained in an xcfx89,1 fashion.
Herein certain terms are used to define certain chemical groups or compounds. These terms are defined below.
A xe2x80x9chydrocarbyl groupxe2x80x9d is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.
By xe2x80x9cnot containing olefinic or acetylenic bondsxe2x80x9d is meant the grouping does not contain olefinic carbon-carbon double bonds (but aromatic rings are not excluded) and carbon-carbon triple bonds.
By xe2x80x9csubstituted hydrocarbylxe2x80x9d herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of xe2x80x9csubstitutedxe2x80x9d are heteroaromatic rings.
By an alkyl aluminum compound is meant a compound in which at least one alkyl group is bound to an aluminum atom. Other groups such as alkoxide, oxygen, and halogen may also be bound to aluminum atoms in the compound.
By xe2x80x9chydrocarbylenexe2x80x9d herein is meant a divalent group containing only carbon and hydrogen. Typical hydrocarbylene groups are xe2x80x94(CH2)4xe2x80x94, xe2x80x94CH2CH(CH2CH3)CH2CH2xe2x80x94 and 
If not otherwise stated, it is preferred that hydrocarbylene groups herein contain 1 to about 30 carbon atoms.
By xe2x80x9csubstituted hydrocarbylenexe2x80x9d herein is meant a hydrocarbylene group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbylene groups herein contain 1 to about 30 carbon atoms. Included within the meaning of xe2x80x9csubstitutedxe2x80x9d are heteroaromatic rings.
By substituted norbornene is meant a norbornene which is substituted with one or more groups which does not interfere substantially with the polymerization. It is preferred that substituent groups (if they contain carbon atoms) contain 1 to 30 carbon atoms. Examples of substituted norbornenes are ethylidene norbornene and methylene norbornene.
By xe2x80x9csaturated hydrocarbylxe2x80x9d is meant a univalent group containing only carbon and hydrogen which contains no unsaturation, such as olefinic, acetylenic, or aromatic groups. Examples of such groups include alkyl and cycloalkyl. If not otherwise stated, it is preferred that saturated hydrocarbyl groups herein contain 1 to about 30 carbon atoms.
By xe2x80x9cneutral Lewis basexe2x80x9d is meant a compound, which is not an ion, which can act as a Lewis base. Examples of such compounds include ethers, amines, sulfides, and organic nitrites.
By xe2x80x9ccationic Lewis acidxe2x80x9d is meant a cation which can act as a Lewis acid. Examples of such cations are sodium and silver cations.
By xe2x80x9cxcex1-olefinxe2x80x9d is meant a compound of the formula CH2xe2x95x90CHR19, wherein R19 is n-alkyl or branched alkyl, preferably n-alkyl.
By xe2x80x9clinear xcex1-olefinxe2x80x9d is meant a compound of the formula CH2xe2x95x90CHR19, wherein Rxc2x7is n-alkyl. It is preferred that the linear xcex1-olefin have 4 to 40 carbon atoms.
By a xe2x80x9csaturated carbon atomxe2x80x9d is meant a carbon atom which is bonded to other atoms by single bonds only. Not included in saturated carbon atoms are carbon atoms which are part of aromatic rings.
By a quaternary carbon atom is meant a saturated carbon atom which is not bound to any hydrogen atoms. A preferred quaternary carbon atom is bound to four other carbon atoms.
By an olefinic bond is meant a carbon-carbon double bond, but does not include bonds in aromatic rings.
By a rare earth metal is meant one of lanthanum, cerium, praeseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
This invention concerns processes for making polymers, comprising, contacting one or more selected olefins or cycloolefins, and optionally an ester or carboxylic acid of the formula CH2xe2x95x90CH(CH2)mCO2R1, and other selected monomers, with a transition metal containing catalyst (and possibly other catalyst components). Such catalysts are, for instance, various complexes of a diimine with these metals. By a xe2x80x9cpolymerization process herein (and the polymers made therein)xe2x80x9d is meant a process which produces a polymer with a degree of polymerization (DP) of about 20 or more, preferably about 40 or more [except where otherwise noted, as in P in compound (VI)] By xe2x80x9cDPxe2x80x9d is meant the average number of repeat (monomer) units in the polymer.
One of these catalysts may generally be written as 
wherein: M is Ni(II), Co(II), Fe(II) or Pd(II); R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; Q is alkyl, hydride, chloride, iodide, or bromide; and S is alkyl, hydride, chloride, iodide, or bromide. Preferably M is Ni(II) or Pd(II).
In a preferred form of (I), R3 and R4 are each independently hydrogen or hydrocarbyl. If Q and/or Sxe2x88x92 is alkyl, it is preferred that the alkyl contains 1 to 4 carbon atoms, and more preferably is methyl.
Another useful catalyst is 
wherein: R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94; Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that, if the donating atom is nitrogen, then the pKa of the conjugate acid of that compound is less than about 6; X is a weakly coordinating anion; and R15 is hydrocarbyl not containing olefinic or acetylenic bonds.
In one preferred form of (II), R3 and R4 are each independently hydrogen or hydrocarbyl. In a more preferred form of (II), T1 is alkyl, and T1 is especially preferably methyl. It is preferred that Z is R62O or R7CN, wherein each R6 is independently hydrocarbyl and R7 is hydrocarbyl. It is preferred that R6 and R7 are alkyl, and it is more preferred that they are methyl or ethyl. It is preferred that X31 is BAF, SbF6, PF6 or BF4.
Another useful catalyst is 
wherein: R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R3 and R4 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbylene, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C (xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94; Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6; X is a weakly coordinating anion; and R15 is hydrocarbyl not containing olefinic or acetylenic bonds.
In one preferred form of (III), R3 and R4 are each independently hydrogen, hydrocarbyl. In a more preferred form of (III) T1 is alkyl, and T1 is especially preferably methyl. It is preferred that Z is R62O or R7CN, wherein each R6 is independently hydrocarbyl and R7 is hydrocarbyl. It is preferred that R6 and R7 are alkyl, and it is especially preferred that they are methyl or ethyl. It is preferred that X is BAFxe2x88x92, SbF6xe2x88x92, PF6xe2x88x92 or BF4xe2x88x92.
Relatively weakly coordinating anions are known to the artisan. Such anions are often bulky anions, particularly those that may delocalize their negative charge. Suitable weakly coordinating anions in this Application include (Ph)4Bxe2x88x92 (Phxe2x95x90phenyl), tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (herein abbreviated BAF), PF6xe2x88x92, BF4xe2x88x92, SbF6xe2x88x92, trifluoromethanesulfonate, p-toluenesulfonate, (RfSO2)2Nxe2x88x92, and (C6F5)4Bxe2x88x92. Preferred weakly coordinating anions include BAFxe2x88x92, PF6xe2x88x92, BF4xe2x88x92, and SbF6xe2x88x92.
Also useful as a polymerization catalyst is a compound of the formula 
wherein: R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R3 and. R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; M is Ni(II) or Pd(II); each R16 is independently hydrogen or alkyl containing 1 to 10 carbon atoms; n is 1, 2, or 3; X is a weakly coordinating anion; and R8 is hydrocarbyl.
It is preferred that n is 3, and all of R16 are hydrogen. It is also preferred that R8 is alkyl or substituted alkyl, especially preferred that it is alkyl, and more preferred that R8 is methyl.
Another useful catalyst is 
wherein: R2 and R5 are hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(xe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94; R15 is hydrocarbyl not containing olefinic or acetylenic bonds; E is halogen or xe2x80x94OR18; R18 is hydrocarbyl not containing olefinic or acetylenic bonds; and X is a weakly coordinating anion. It is preferred that T1 is alkyl containing 1 to 4 carbon atoms, and more preferred that it is methyl. In other preferred compounds (V), R3 and R4 are methyl or hydrogen and R2 and R5 are 2,6-diisopropylphenyl and X is BAF. It is also preferred that E is chlorine.
Another useful catalyst is a compound of the formula 
wherein: R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; T2 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R15C (xe2x95x90O)xe2x80x94 or R15OC (xe2x95x90O)xe2x80x94; R15 is hydrocarbyl not containing olefinic or acetylenic bonds; and X is a weakly coordinating anion. In a more preferred form of (VII), T2 is alkyl containing 1 to 4 carbon atoms and T2 is especially preferably methyl. It is preferred that X is perfluoroalkylsulfonate, especially trifluoromethanesulfonate (triflate). If Xxe2x88x92 is an extremely weakly coordinating anion such as BAF, (VII) may not form. Thus it may be said that (VII) forms usually with weakly, but perhaps not extremely weakly, coordinating anions.
In all compounds, intermediates, catalysts, processes, etc. in which they appear it is preferred that R2 and R5 are each independently hydrocarbyl, and in one form it is especially preferred that R2 and R5 are both 2,6-diisopropylphenyl, particularly when R3 and R4 are each independently hydrogen or methyl. It is also preferred that R3 and R4 are each independently hydrogen, hydrocarbyl or taken together hydrocarbylene to form a carbocyclic ring.
Compounds of the formula (I) wherein M is Pd, Q is alkyl and S is halogen may be made by the reaction of the corresponding 1,5-cyclooctadiene (COD) Pd complex with the appropriate diimine. When M is Ni, (I) can be made by the displacement of a another ligand, such as a dialkylether or a polyether such as 1,2-dimethoxyethane, by an appropriate diimine.
Catalysts of formula (II), wherein Xxe2x88x92 is BAF, may be made by reacting a compound of formula (I) wherein Q is alkyl and S is halogen, with about one equivalent of an alkali metal salt, particularly the sodium salt, of HBAF, in the presence of a coordinating ligand, particularly a nitrile such as acetonitrile. When Xxe2x88x92 is an anion such as BAFxe2x88x92, SbF6xe2x88x92 or BF4xe2x88x92 the same starting palladium compound can be reacted with the silver salt AgX.
However, sometimes the reaction of a diimine with a 1,5-COD Pd complex as described above to make compounds of formula (II) may be slow and/or give poor conversions, thereby rendering it difficult to make the starting material for (II) using the method described in the preceding paragraph. For instance when: R2xe2x95x90R5xe2x95x90Ph2CHxe2x80x94 and R3xe2x95x90R4xe2x95x90H; R2xe2x95x90R5xe2x95x90Phxe2x80x94 and R3xe2x95x90R4xe2x95x90Ph; R2xe2x95x90R5xe2x95x902-t-butylphenyl and R3xe2x95x90R4xe2x95x90CH3; R2xe2x95x90R5xe2x95x90xcex1-naphthyl and R3xe2x95x90R4xe2x95x90CH3; and R2xe2x95x90R550 2-phenylphenyl and R3xe2x95x90R4xe2x95x90CH3 difficulty may be encountered in making a compound of formula (II).
In these instances it has been found more convenient to prepare (II) by reacting [(xcex74-1,5-COD)PdT1Z]+Xxe2x88x92, wherein T1 and X are as defined above and Z is an organic nitrile ligand, preferably in an organic nitrile solvent, with a diimine of the formula 
By a xe2x80x9cnitrile solventxe2x80x9d is meant a solvent that is at least 20 volume percent nitrile compound. The product of this reaction is (II), in which the Z ligand is the nitrile used in the synthesis. In a preferred synthesis, T1 is methyl and the nitrile used is the same as in the starting palladium compound, and is more preferably acetonitrile. The process is carried out in solution, preferably when the nitrile is substantially all of the solvent, at a temperature of about xe2x88x9240xc2x0 C. to about +60xc2x0 C., preferably about 0xc2x0 C. to about 30xc2x0 C. It is preferred that the reactants be used in substantially equimolar quantities.
The compound [(xcex74-1,5-COD)PdT1Z]+Xxe2x88x92, wherein T1 is alkyl, Z is an organic nitrile and X is a weakly coordinating anion may be made by the reaction of [(xcex74-1,5-COD)PdT1A, wherein A is Cl, Br or I and T1 is alkyl with the silver salt of Xxe2x88x92, AgX, or if X is BAF with an alkali metal salt of HBAF, in the presence of an organic nitrile, which of course will become the ligand T1. In a preferred process A is Cl, T1 is alkyl, more preferably methyl, and the organic nitrile is an alkyl nitrile, more preferably acetonitrile. The starting materials are preferably present in approximately equimolar amounts, except for the nitrile which is present preferably in excess. The solvent is preferably a non-coordinating solvent such as a halocarbon. Methylene chloride is useful as such a solvent. The process preferably is carried out at a temperature of about xe2x88x9240xc2x0 C. to about +50xc2x0 C. It is preferred to exclude water and other hydroxyl containing compounds from the process, and this may be done by purification of the ingredients and keeping the process mass under an inert gas such as nitrogen.
Compounds of formula (II) [or (III) when the metal is nickel] can also be made by the reaction of 
with a source of the conjugate acid of the anion X, the acid HX or its equivalent (such as a trityl salt) in the presence of a solvent which is a weakly coordinating ligand such as a dialkyl ether or an alkyl nitrile. It is preferred to carry out this reaction at about xe2x88x9280xc2x0 C. to about 30xc2x0 C.
Compounds of formula (XXXXI) can be made by a process, comprising, contacting, at a temperature of about xe2x88x9280xc2x0 C. to about +20xc2x0 C., a compound of the formula xcex74-1,5-COD)PdMe2 and a diimine of the formula 
wherein: COD is 1,5-cyclooctadiene; R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; and R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring. It is preferred that the temperature is about xe2x88x9250xc2x0 C. to about +10xc2x0 C. It is also preferred that the two starting materials be used in approximately equimolar quantities, and/or that the reaction be carried out in solution. It is preferred that R2 and R5 are both 2-t-butylphenyl or 2,5-di-t-butylphenyl and that R3 and R4 taken together are An, or R3 and R4 are both hydrogen or methyl.
Compounds of formula (IV) can be made by several routes. In one method a compound of formula (II) is reacted with an acrylate ester of the formula CH2xe2x95x90CHCO2R1 wherein R1 is as defined above. This reaction is carried out in a non-coordinating solvent such as methylene chloride, preferably using a greater than 1 to 50 fold excess of the acrylate ester. In a preferred reaction, Q is methyl, and R1 is alkyl containing 1 to 4 carbon atoms, more preferably methyl. The process is carried out at a temperature of about xe2x88x92100xc2x0 C. to about +100xc2x0 C., preferably about 0xc2x0 C. to about 50xc2x0 C. It is preferred to exclude water and other hydroxyl containing compounds from the process, and this may be done by purification of the ingredients and keeping the process mass under an inert gas such as nitrogen.
Alternatively, (IV) may be prepared by reacting (I), wherein Q is alkyl and S is Cl, Br or I with a source of an appropriate weakly coordinating anion such as AgX or an alkali metal salt of BAF and an acrylate ester (formula as immediately above) in a single step. Approximately equimolar quantities of (I) and the weakly coordinating anion source are preferred, but the acrylate ester may be present in greater than 1 to 50 fold excess. In a preferred reaction, Q is methyl, and R1 is alkyl containing 1 to 4 carbon atoms, more preferably methyl. The process is preferably carried out at a temperature of about xe2x88x92100xc2x0 C. to about +100xc2x0 C., preferably about 0xc2x0 C. to about 50xc2x0 C. It is preferred to exclude water and other hydroxyl containing compounds from the process, and this may be done by purification of the ingredients and keeping the process mass under an inert gas such as nitrogen.
In another variation of the preparation of (IV) from (I) the source of the weakly coordinating anion is a compound which itself does not contain an anion, but which can combine with S [of (I)] to form such a weakly coordinating anion. Thus in this type of process by xe2x80x9csource of weakly coordinating anionxe2x80x9d is meant a compound which itself contains the anion which will become Xxe2x88x92, or a compound which during the process can combine with other process ingredients to form such an anion.
Catalysts of formula (V), wherein Xxe2x88x92 is BAFxe2x88x92, may be made by reacting a compound of formula (I) wherein Q is alkyl and S is halogen, with about one-half of an equivalent of an alkali metal salt, particularly the sodium salt, of HBAF. Alternatively, (V) containing other anions may be prepared by reacting (I), wherein Q is alkyl and S is Cl, Br or I with one-half equivalent of a source of an appropriate weakly coordinating anion such as AgX.
Some of the nickel and palladium compounds described above are useful in processes for polymerizing various olefins, and optionally also copolymerizing olefinic esters, carboxylic acids, or other functional olefins, with these olefins. When (I) is used as a catalyst, a neutral Lewis acid or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion is also present as part of the catalyst system (sometimes called a xe2x80x9cfirst compoundxe2x80x9d in the claims). By a xe2x80x9cneutral Lewis acidxe2x80x9d is meant a compound which is a Lewis acid capable for abstracting Qxe2x88x92 or Sxe2x88x92 from (I) to form a weakly coordination anion. The neutral Lewis acid is originally uncharged (i.e., not ionic). Suitable neutral Lewis acids include SbF5, Ar3B (wherein Ar is aryl), and BF3. By a cationic Lewis acid is meant a cation with a positive charge such as Ag+, H+, and Na+.
In those instances in which (I) (and similar catalysts which require the presence of a neutral Lewis acid or a cationic Lewis or Bronsted acid), does not contain an alkyl or hydride group already bonded to the metal (i.e., neither Qxe2x88x92 or S is alkyl or hydride), the neutral Lewis acid or a cationic Lewis or Bronsted acid also alkylates or adds a hydride to the metal, i.e., causes an alkyl group or hydride to become bonded to the metal atom.
A preferred neutral Lewis acid, which can alkylate the metal, is a selected alkyl aluminum compound, such as R93Al, R92AlCl, R9AlCl2, and xe2x80x9cR9AlOxe2x80x9d (alkylaluminoxanes), wherein R9 is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4 carbon atoms. Suitable alkyl aluminum compounds include methylaluminoxane (which is an oligomer with the general formula [MeAlO]n), (C2H5)2AlCl, C2H5AlCl2, and [(CH3)2CHCH2]3Al.
Metal hydrides such as NaBH4 may be used to bond hydride groups to the metal M.
The first compound and (I) are contacted, usually in the liquid phase, and in the presence of the olefin, and/or 4-vinylcyclohexene, cyclopentene, cyclobutene, substituted norbornene, or norbornene. The liquid phase may include a compound added just as a solvent and/or may include the monomer(s) itself. The molar ratio of first compound:nickel or palladium complex is about 5 to about 1000, preferably about 10 to about 100. The temperature at which the polymerization is carried out is about xe2x88x92100xc2x0 C. to about +200xc2x0 C., preferably about xe2x88x9220xc2x0 C. to about +80xc2x0 C. The pressure at which the polymerization is carried out is not critical, atmospheric pressure to about 275 MPa, or more, being a suitable range. The pressure may affect the microstructure of the polyolefin produced (see below).
When using (I) as a catalyst, it is preferred that R3 and R4 are hydrogen, methyl, or taken together are 
It is also preferred that both R2 and R5 are 2,6-diisopropylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 4-methylphenyl, phenyl, 2,4,6-trimethylphenyl, and 2-t-butylphenyl. When M is Ni(II), it is preferred that Q and S are each independently chloride or bromide, while when M is Pd(II) it is preferred that Q is methyl, chloride, or bromide, and S is chloride, bromide or methyl. In addition, the specific combinations of groups in the catalysts listed in Table I are especially preferred.
Preferred olefins in the polymerization are one or more of ethylene, propylene, 1-butene, 2-butene, 1-hexene 1-octene, 1-pentene, 1-tetradecene, norbornene, and cyclopentene, with ethylene, propylene and cyclopentene being more preferred. Ethylene (alone as a homopolymer) is specially preferred.
The polymerizations with (I) may be run in the presence of various liquids, particularly aprotic organic liquids. The catalyst system, monomer(s), and polymer may be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from occurring. Suitable liquids include alkanes, cycloalkanes, selected halogenated hydrocarbons, and aromatic hydrocarbons. Specific useful solvents include hexane, toluene and benzene.
Whether such a liquid is used, and which and how much liquid is used, may affect the product obtained. It may affect the yield, microstructure, molecular weight, etc., of the polymer obtained.
Compounds of formulas (XI), (XIII), (XV) and (XIX) may also be used as catalysts for the polymerization of the same monomers as compounds of formula (I). The polymerization conditions are the same for (XI), (XIII), (XV) and (XIX) as for (I), and the same Lewis and Bronsted acids are used as co-catalysts. Preferred groupings R2, R3, R4, and R5 (when present) in (XI) and (XIII) are the same as in (I), both in a polymerization process and as compounds in their own right.
Preferred (XI) compounds have the metals Sc(III), Zr(IV), Ni(II), Ni(I), Pd(II), Fe(II), and Co(II). When M is Zr, Ti, Fe, and Sc it is preferred that all of Q and S are chlorine or bromine more preferably chlorine. When M is Ni or Co it is preferred that all of Q and S are chlorine, bromine or iodine, more preferably bromine.
In (XVII) preferred metals are Ni(II) and Ti(IV). It is preferred that all of Q and S are halogen. It is also preferred that all of R28, R29, and R30 are hydrogen, and/or that both R44 and R45 are 2,4,6-trimethylphenyl or 9-anthracenyl.
In (XV) it is preferred that both of R31 are hydrogen.
In (XIII), (XXIII) and (XXXII) (as polymerization catalysts and as novel compounds) it is preferred that all of R20, R21, R22 and R23 are methyl. It is also preferred that T1 and T2 are methyl. For (XIII), when M is Ni(I) or (II), it is preferred that both Q and S are bromine, while when M is Pd it is preferred that Q is methyl and S is chlorine.
Compounds (II), (IV) or (VII) will each also cause the polymerization of one or more of an olefin, and/or a selected cyclic olefin such as cyclobutene, cyclopentene or norbornene, and, when it is a Pd(II) complex, optionally copolymerize an ester or carboxylic acid of the formula CH2xe2x95x90CH(CH2)mCO2R1, wherein m is 0 or an integer of 1 to 16 and R1 is hydrogen or hydrocarbyl or substituted hydrocarbyl, by themselves (without cocatalysts). However, (III) often cannot be used when the ester is present. When norbornene or substituted norbornene is present no other monomer should be present.
Other monomers which may be used with compounds (II), (IV) or (VII) (when it is a Pd(II) complex) to form copolymers with olefins and selected cycloolefins are carbon monoxide (CO), and vinyl ketones of the general formula H2Cxe2x95x90CHC(O)R25, wherein R25 is alkyl containing 1 to 20 carbon atoms, and it is preferred that R25 is methyl. In the case of the vinyl ketones, the same compositional limits on the polymers produced apply as for the carboxylic acids and esters described as comonomers in the immediately preceding paragraph.
CO forms alternating copolymers with the various olefins and cycloolefins which may be polymerized with compounds (II), (IV) or (VII). The polymerization to form the alternating copolymers is done with both CO and the olefin simultaneously in the process mixture, and available to the catalyst. It is also possible to form block copolymers containing the alternating CO/(cyclo)olefin copolymers and other blocks containing just that olefin or other olefins or mixtures thereof. This may be done simply by sequentially exposing compounds (II), (IV) or (VII), and their subsequent living polymers, to the appropriate monomer or mixture of monomers to form the desired blocks. Copolymers of CO, a (cyclo)olefin and a saturated carboxylic acid or ester of the formula CH2xe2x95x90CH(CH2)mCO2R1, wherein m is 0 or an integer of 1 to 16 and R1 is hydrogen or hydrocarbyl or substituted hydrocarbyl, may also be made by simultaneously exposing the polymerization catalyst or living polymer to these 3 types of monomers.
The polymerizations may be carried out with (II), (III), (IV) or (VII), and other catalyst molecules or combinations, initially in the solid state [assuming (II), (III) (IV) or (VII) is a solid] or in solution. The olefin and/or cycloolefin may be in the gas or liquid state (including gas dissolved in a solvent). A liquid, which may or may not be a solvent for any or all of the reactants and/or products may also be present. Suitable liquids include alkanes, cycloalkanes, halogenated alkanes and cycloalkanes, ethers, water, and alcohols, except that when (III) is used, hydrocarbons should preferably be used as solvents. Specific useful solvents include methylene chloride, hexane, CO2, chloroform, perfluoro(n-butyltetrahydrofuran) (herein sometimes called FC-75), toluene, dichlorobenzene, 2-ethylhexanol, and benzene.
It is particularly noteworthy that one of the liquids which can be used in this polymerization process with (II), (III), (IV) or (VII) is water, see for instance Examples 213-216. Not only can water be present but the polymerization xe2x80x9cmediumxe2x80x9d may be largely water, and various types of surfactants may be employed so that an emulsion polymerization may be done, along with a suspension polymerization when surfactants are not employed.
Preferred olefins and cycloolefins in the polymerization using (II), (III) or (IV) are one or more of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-butene, cyclopentene, 1-tetradecene, and norbornene; and ethylene, propylene and cyclopentene are more preferred. Ethylene alone is especially preferred.
Olefinic esters or carboxylic acids of the formula CH2xe2x95x90CH(CH2)mCO2R1, wherein R1 is hydrogen, hydrocarbyl, or substituted hydrocarbyl, and m is 0 or an integer of 1 to 16. It is preferred if R1 hydrocarbyl or substituted hydrocarbyl and it is more preferred if it is alkyl containing 1 to 10 carbon atoms, or glycidyl. It is also preferred if m is 0 and/or R1 is alkyl containing 1 to 10 carbon atoms. It is preferred to make copolymers containing up to about 60 mole percent, preferably up to about 20 mole percent of repeat units derived from the olefinic ester or carboxylic acid. Total repeat unit units in the polymer herein refer not only to those in the main chain from each monomer unit, but those in branches or side chains as well.
When using (II), (III), (IV) or (VII) as a catalyst it is preferred that R3 and R4 are hydrogen, methyl, or taken together are 
It is also preferred that both R2 and R5 are 2,6-diisopropylphenyl, 2,6-dimethylphenyl, 4-methylphenyl, phenyl, 2,6-diethylphenyl, 2,4,6-trimethylphenyl and 2-t-butylphenyl. When (II) is used, it is preferred that T1 is methyl, R6 is methyl or ethyl and R7 is methyl. When (III) is used it is preferred that T1 is methyl and said Lewis base is R62O, wherein R6 is methyl or ethyl. When (IV) is used it is preferred that R8 is methyl, n is 3 and R16 is hydrogen. In addition in Table II are listed all particularly preferred combinations as catalysts for (II), (III), (IV) and (VII).
When using (II), (III), (IV) or (VII) the temperature at which the polymerization is carried out is about xe2x88x92100xc2x0 C. to about +200xc2x0 C., preferably about 0xc2x0 C. to about 150xc2x0 C., more preferably about 25xc2x0 C. to about 100xc2x0 C. The pressure at which the polymerization is carried out is not critical, atmospheric pressure to about 275 MPa being a suitable range. The pressure can affect the microstructure of the polyolefin produced (see below).
Catalysts of the formulas (II), (III), (IV) and (VII) may also be supported on a solid catalyst (as opposed to just being added as a solid or in solution), for instance on silica gel (see Example 98). By supported is meant that the catalyst may simply be carried physically on the surface of the solid support, may be adsorbed, or carried by the support by other means.
When using (XXX) as a ligand or in any process or reaction herein it is preferred that n is 2, all of R30, R28 and R29 are hydrogen, and both of R44 and R45 are 9-anthracenyl.
Another polymerization process comprises contacting a compound of the formula [Pd(R13CN)4]X2 or a combination of Pd[OC(O)R40]2 and HX, with a compound of the formula 
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclopentene, cyclobutene, substituted norbornene and norbornene, wherein: R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring; each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that R17 contains no olefinic bonds; R40 is hydrocarbyl or substituted hydrocarbyl; and X is a weakly coordinating anion; provided that when norbornene or substituted norbornene is present no other monomer is present.
It is believed that in this process a catalyst similar to (II) may be initially generated, and this then causes the polymerization. Therefore, all of the conditions, monomers (including olefinic esters and carboxylic acids), etc., which are applicable to the process using (II) as a polymerization catalyst are applicable to this process. All preferred items are also the same, including appropriate groups such as R2, R3, R4, R5, and combinations thereof. This process however should be run so that all of the ingredients can contact each other, preferably in a single phase. Initially at least, it is preferred that this is done in solution. The molar ratio of (VIII) to palladium compound used is not critical, but for most economical use of the compounds, a moderate excess, about 25 to 100% excess, of (VIII) is preferably used.
As mentioned above, it is believed that in the polymerization using (VIII) and [Pd(R13CN)4]X2 or a Pd[II] carboxylate a catalyst similar to (II) is formed. Other combinations of starting materials that can combine into catalysts similar to (II), (III), (IV) and (VII) often also cause similar polymerizations, see for instance Examples 238 and 239. Also combinations of xcex1-diimines or other diimino ligands described herein with: a nickel [0] or nickel [I] compound, oxygen, an alkyl aluminum compound and an olefin; a nickel [0] or nickel [I] compound, an acid such as HX and an olefin; or an xcex1-diimine Ni[0] or nickel [I] complex, oxygen, an alkyl aluminum compound and an olefin. Thus active catalysts from xcex1-diimines and other bidentate imino compounds can be formed beforehand or in the same xe2x80x9cpotxe2x80x9d (in situ) in which the polymerization takes place. In all of the polymerizations in which the catalysts are formed in situ, preferred groups on the xcex1-diimines are the same as for the preformed catalysts.
In general Ni[0], Ni[I] or Ni(II) compounds may be used as precursors to active catalyst species. They must have ligands which can be displaced by the appropriate bidentate nitrogen ligand, or must already contain such a bidentate ligand already bound to the nickel atom. Ligands which may be displaced include 1,5-cyclooctadiene and tris(o-tolyl)phosphite, which may be present in Ni[0] compounds, or dibenzylideneacetone, as in the useful Pd[0] precursor tris(dibenzylideneacetone)dipalladium[0]. These lower valence nickel compounds are believed to be converted into active Ni[II] catalytic species. As such they must also be contacted (react with) with an oxidizing agent and a source of a weakly coordinating anion (Xxe2x88x92). Oxidizing agents include oxygen, HX (wherein X is a weakly coordinating anion), and other well known oxidizing agents. Sources of Xxe2x88x92 include HX, alkylaluminum compounds, alkali metal and silver salts of Xxe2x88x92. As can be seen above, some compounds such as HX may act as both an oxidizing agent and a source of Xxe2x88x92. Compounds containing other lower valent metals may be converted into active catalyst species by similar methods.
When contacted with an alkyl aluminum compound or HX useful Ni[0] compounds include 
Various types of Ni[0] compounds are known in the literature. Below are listed references for the types shown immediately above.
(XXXIII) G. van Koten, et al., Adv. Organometal. Chem., vol. 21, p. 151-239 (1982).
(XXXXII) W. Bonrath, et al., Angew. Chem. Int. Ed. Engl., vol. 29, p. 298-300 (1990).
(XXXXIV) H. tom Dieck, et al., Z. Natruforsch., vol. 366, p. 823-832 (1981); and M. Svoboda, et al., J. Organometal. Chem., vol. 191, p. 321-328 (1980).
(XXXXV) G. van Koten, et al., Adv. Organometal. Chem., vol. 21, p. 151-239 (1982).
In polymerizations using (XIV), the same preferred monomers and groups (such as R2, R3, R4, R5 and X) as are preferred for the polymerization using (II) are used and preferred. Likewise, the conditions used and preferred for polymerizations with (XIV) are similar to those used and preferred for (II), except that higher olefin pressures (when the olefin is a gas) are preferred. Preferred pressures are about 2.0 to about 20 MPa. (XIV) may be prepared by the reaction of one mole of [Pd(R13CN)4]X2 with one mole of (VIII) in acetonitrile or nitromethane.
Novel compound (XIV) is used as an olefin polymerization catalyst. In preferred forms of (XIV), the preferred groups R2, R3, R4, R5and X are the same as are preferred for compound (II).
Another type of compound which is an olefin polymerization catalyst are xcfx80-allyl and xcfx80-benzyl compounds of the formula 
wherein M is Ni(II) or Pd(II); R2 and R5 are hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; X is a weakly coordinating anion; and A is a xcfx80-allyl or xcfx80-benzyl group. By a xcfx80-allyl group is meant a monoanionic with 3 adjacent sp2 carbon atoms bound to a metal center in an xcex73 fashion. The three sp2 carbon atoms may be substituted with other hydrocarbyl groups or functional groups. Typical xcfx80-allyl groups include 
wherein R is hydrocarbyl. By a xcfx80-benzyl group is meant xcfx80-allyl ligand in which two of the sp2 carbon atoms are part of an aromatic ring. Typical xcfx80-benzyl groups include 
xcfx80-Benzyl compounds usually initiate polymerization of the olefins fairly readily even at room temperature, but xcfx80-allyl compounds may not necessarily do so. Initiation of xcfx80-allyl compounds can be improved by using one or more of the following methods:
Using a higher temperature such as about 80xc2x0 C.
Decreasing the bulk of the xcex1-diimine ligand, such as R2 and R5 being 2,6-dimethylphenyl instead of 2,6-diisopropylphenyl.
Making the xcfx80-allyl ligand more bulky, such as using 
xe2x80x83rather than the simple xcfx80-allyl group itself.
Having a Lewis acid present while using a functional xcfx80-allyl or xcfx80-benzyl group. Relatively weak Lewis acids such a triphenylborane, tris(pentafluorophenyl)borane, and tris(3,5-trifluoromethylphenyl)borane, are preferred. Suitable functional groups include chloro and ester. xe2x80x9cSolidxe2x80x9d acids such as montmorillonite may also be used.
When using (XXXVII) as a polymerization catalyst, it is preferred that ethylene and/or a linear xcex1-olefin is the monomer, or cyclopentene, more preferred if the monomer is ethylene and/or propylene, and ethylene is especially preferred. A preferred temperature for the polymerization process using (XXXVII) is about +20xc2x0 C. to about 100xc2x0 C. It is also preferred that the partial pressure due to ethylene or propylene monomer is at least about 600 kPa. It is also noted that (XXXVII) is a novel compound, and preferred items for (XXXVII) for the polymerization process are also preferred for the compound itself.
Another catalyst for the polymerization of olefins is a compound of the formula 
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene,
wherein: R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; R54 is hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; each R55 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group; W is alkylene or substituted alkylene containing 2 or more carbon atoms; Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6, or an olefin of the formula R17CHxe2x95x90CHR17; each R17 is independently alkyl or substituted alkyl; and X is a weakly coordinating anion. It is preferred that in compound (XXXVIII) that: R54 is phenyl or substituted phenyl, and preferred substituents are alkyl groups; each R56 is independently hydrogen or alkyl containing 1 to 10 carbon atoms; W contains 2 carbon atoms between the phenyl ring and metal atom it is bonded to or W is a divalent polymeric group derived from the polymerization of R17CHxe2x95x90CHR17, and it is especially preferred that it is xe2x80x94CH(CH3)CH2xe2x80x94 or xe2x80x94C(CH3)2CH2xe2x80x94; and Z is a dialkyl ether or an olefin of the formula R17CHxe2x95x90CHR17; and combinations thereof. W is an alkylene group in which each of the two free valencies are to different carbon atoms of the alkylene group.
When W is a divalent group formed by the polymerization of R17CHxe2x95x90CHR17, and Z is R17CHxe2x95x90CHR17, the compound (XXXVIII) is believed to be a living ended polymer. That end of W bound to the phenyl ring actually is the original fragment from R56 from which the xe2x80x9cbridgexe2x80x9d W originally formed, and the remaining part of W is formed from the olefin(s) R17CHxe2x95x90CHR17. In a sense this compound is similar in function to compound (VI).
By substituted phenyl in (XXXVIII) and (XXXIX) is meant the phenyl ring can be substituted with any grouping which does not interfere with the compound""s stability or any of the reactions the compound undergoes. Preferred substituents in substituted phenyl are alkyl groups, preferably containing 1 to 10 carbon atoms.
Preferred monomers for this polymerization are ethylene and linear xcex1-olefins, or cyclopentene, particularly propylene, and ethylene and propylene or both are more preferred, and ethylene is especially preferred.
It is noted that (XXXVIII) is a novel compound, and preferred compounds and groupings are the same as in the polymerization process.
Compound (XXXVIII) can be made by heating compound (XXXIX), 
wherein: R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; R54 is hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; each R55 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group; R56 is alkyl containing 2 to 30 carbon atoms; T3 is alkyl; Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6; and X is a weakly coordinating anion. Preferred groups are the same as those in (XXXVIII). In addition it is preferred that T5 contain 1 to 10 carbon atoms, and more preferred that it is methyl. A preferred temperature for the conversion of (XXXIX) to (XXXVIII) is about xe2x88x9230xc2x0 C. to about 50xc2x0 C. Typically the reaction takes about 10 min. to about 5 days, the higher the temperature, the faster the reaction. Another factor which affects the reaction rate is the nature of Z. The weaker the Lewis basicity of Z, the faster the desired reaction will be.
When (II), (III), (IV), (V), (VII), (VIII) or a combination of compounds that will generate similar compounds, (subject to the conditions described above) is used in the polymerization of olefins, cyclolefins, and optionally olefinic esters or carboxylic acids, polymer having what is believed to be similar to a xe2x80x9cliving endxe2x80x9d is formed. This molecule is that from which the polymer grows to its eventual molecular weight. This compound may have the structure 
wherein: M is Ni(II) or Pd(II); R2 and R5 are hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R11 is independently hydrogen, alkyl or xe2x80x94(CH2)mCO2R1; T3 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15 (Cxe2x95x90O)xe2x80x94, R15O(Cxe2x95x90O)xe2x80x94, or xe2x80x94CH2CH2CH2CO2R8; R15 is hydrocarbyl not containing olefinic or acetylenic unsaturation; P is a divalent group containing one or more repeat units derived from the polymerization of one or more of ethylene, an olefin of the formula R17CHxe2x95x90CH2 or R17CHxe2x95x90CHR17, cyclobutene, cyclopentene, substituted norbornene, or norbornene and, when M is Pd(II), optionally one or more compounds of the formula CH2xe2x95x90CH(CH2)mCO2R1; R8 is hydrocarbyl; each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; m is 0 or an integer from 1 to 16; R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms; and X is a weakly coordinating anion; and that when M is Ni(II), R11 is not xe2x80x94CO2R8 and when M is Pd a diene is not present. By an xe2x80x9colefinic ester or carboxylic acidxe2x80x9d is meant a compound of the formula CH2xe2x95x90CH(CH2)mCO2R1, wherein m and R1 are as defined immediately above.
This molecule will react with additional monomer (olefin, cyclic olefin, olefinic ester or olefinic carboxylic acid) to cause further polymerization. In other words, the additional monomer will be added to P, extending the length of the polymer chain. Thus P may be of any size, from one xe2x80x9crepeat unitxe2x80x9d to many repeat units, and when the polymerization is over and P is removed from M, as by hydrolysis, P is essentially the polymer product of the polymerization. Polymerizations with (VI), that is contact of additional monomer with this molecule takes place under the same conditions as described above for the polymerization process using (II), (III), (IV), (V), (VII) or (VIII), or combinations of compounds that will generate similar molecules, and where appropriate preferred conditions and structures are the same.
The group T3 in (VI) was originally the group T1 in (II) or (III), or the group which included R8 in (IV). It in essence will normally be one of the end groups of the eventual polymer product. The olefinic group which is coordinated to M, R11CHxe2x95x90CHR11 is normally one of the monomers, olefin, cyclic olefin, or, if Pd(II) is M, an olefinic ester or carboxylic acid. If more than one of these monomers is present in the reaction, it may be any one of them. It is preferred that T3 is alkyl and especially preferred that it is methyl, and it is also preferred that R11 is hydrogen or n-alkyl. It is also preferred that M is Pd(II).
Another xe2x80x9cformxe2x80x9d for the living end is (XVI). 
This type of compound is sometimes referred to as a compound in the xe2x80x9cagostic statexe2x80x9d. In fact both (VI) and (XVI) may coexist together in the same polymerization, both types of compound representing living ends. It is believed that (XVI)-type compounds are particularly favored when the end of the growing polymer chain bound to the transition metal is derived from a cyclic olefin such as cyclopentene. Expressed in terms of the structure of (XVI) this is when both of R11 are hydrocarbylene to form a carbocyclic ring, and it is preferred that this be a five-membered carbocyclic ring.
For both the polymerization process using (XVI) and the structure of (XVI) itself, the same conditions and groups as are used and preferred for (VI) are also used and preferred for (XVI), with the exception that for R11 it is preferred in (XVI) that both of R11 are hydrocarbylene to form a carbocyclic ring.
This invention also concerns a compound of the formula 
wherein: M is Ni(II) or Pd(II); R2 and R5 are hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; R1 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R14 is independently hydrogen, alkyl or [when M is Pd(II)] xe2x80x94(CH2)mCO2R1; R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms; T4 is alkyl, xe2x80x94R60C(O)OR2, R15(Cxe2x95x90O)xe2x80x94 or R15OC(xe2x95x90O)xe2x80x94; R15 is hydrocarbyl not containing olefinic or acetylenic bonds; R60 is alkylene not containing olefinic or acetylenic bonds; R8 is hydrocarbyl; and X is a weakly coordinating anion.
(IX) may also be used to polymerize olefins, cyclic olefins, and optionally olefinic esters and carboxylic acids. The same conditions (except as noted below) apply to the polymerizations using (IX) as they do for (VI). It is preferred that M is Pd(II) and T4 is methyl.
A compound of formula (V) may also be used as a catalyst for the polymerization of olefins, cyclic olefins, and optionally olefinic esters and/or carboxylic acids. In this process (V) is contacted with one or more of the essential monomers. Optionally a source of a relatively weakly coordinating anion may also be present. Such a source could be an alkali metal salt of BAF or AgX (wherein X is the anion), etc. Preferably about 1 mole of the source of X, such as AgX, will be added per mole of (V). This will usually be done in the liquid phase, preferably in which (V) and the source of the anion are at least partially soluble. The conditions of this polymerization are otherwise the same as described above for (II), (III), (IV) and (VII), including the preferred conditions and ingredients.
In polymerizations using (XX) as the catalyst, a first compound which is a source of a relatively noncoordinating monoanion is present. Such a source can be an alkali metal or silver salt of the monoanion. 
It is preferred that the alkali metal cation is sodium or potassium. It is preferred that the monoanion is SbF6, BAF, PF6, or BF4xe2x88x92, and more preferred that it is BAF. It is preferred that T1 is methyl and/or Sxe2x88x92 is chlorine. All other preferred groups and conditions for these polymerizations are the same as for polymerizations with (II).
In all of the above polymerizations, and the catalysts for making them it is preferred that R2 and R5, if present, are 2,6-diisopropylphenyl and R3 and R4 are hydrogen or methyl. When cyclopentene is polymerized, is preferred that R2 and R5 (if present) are 2,6-dimethylphenyl or 2,4,6-trimethylphenyl and that R3 and R4 taken together are An. R2, R3, R4 and R5 and other groups herein may also be substituted hydrocarbyl. As previously defined, the substituent groups in substituted hydrocarbyl groups (there may be one or more substituent groups) should not substantially interfere with the polymerization or other reactions that the compound is undergoing. Whether a particular group will interfere can first be judged from the artisans general knowledge and the particular polymerization or other reaction that is involved. For instance, in polymerizations where an alkyl aluminum compound is used may not be compatible with the presence of groups containing an active (relatively acidic) hydrogen atom, such as hydroxyl or carboxyl because of the known reaction of alkyl aluminum compounds with such active hydrogen containing groups (but such polymerizations may be possible if enough xe2x80x9cextraxe2x80x9d alkyl aluminum compound is added to react with these groups). However, in very similar polymerizations where alkyl aluminum compounds are not present, these groups containing active hydrogen may be present. Indeed many of the polymerization processes described herein are remarkably tolerant to the presence of various functional groups. Probably the most important considerations as to the operability of compounds containing any particular functional group are the effect of the group on the coordination of the metal atom (if present), and side reaction of the group with other process ingredients (such as noted above). Therefore of course, the further away from the metal atom the functional group is, the less likely it is to influence, say, a polymerization. If there is doubt as to whether a particular functional group, in a particular position, will affect a reaction, simple minimal experimentation will provide the requisite answer. Functional groups which may be present in R2, R3, R4, R5, and other similar radicals herein include hydroxy, halo (fluoro, chloro, bromo and iodo), ether, ester, dialkylamino, carboxy, oxo (keto and aldehyo), nitro, amide, thioether, and imino. Preferred functional groups are hydroxy, halo, ether and dialkylamino.
Also in all of the polymerizations, the (cyclo)olefin may be substituted hydrocarbyl. Suitable substituents include ether, keto, aldehyde, ester, carboxylic acid.
In all of the above polymerizations, with the exceptions noted below, the following monomer(s), to produce the corresponding homo- or copolymers, are preferred to be used: ethylene; propylene; ethylene and propylene; ethylene and an xcex1-olefin; an xcex1-olefin; ethylene and an alkyl acrylate, especially methyl acrylate; ethylene and acrylic acid; ethylene and carbon monoxide; ethylene, and carbon monoxide and an acrylate ester or acrylic acid, especially methyl acrylate; propylene and alkyl acrylate, especially methyl acrylate; cyclopentene; cyclopentene and ethylene; cyclopentene and propylene. Monomers which contain a carbonyl group, including esters, carboxylic acids, carbon monoxide, vinyl ketones, etc., can be polymerized with Pd(II) containing catalysts herein, with the exception of those that require the presence of a neutral or cationic Lewis acid or cationic Bronsted acid, which is usually called the xe2x80x9cfirst compoundxe2x80x9d in claims describing such polymerization processes.
Another useful xe2x80x9cmonomerxe2x80x9d for these polymerization processes is a C4 refinery catalytic cracker stream, which will often contain a mixture of n-butane, isobutane, isobutene, 1-butene, 2-butenes and small amounts of butadiene. This type of stream is referred to herein as a xe2x80x9ccrude butenes streamxe2x80x9d. This stream may act as both the monomer source and xe2x80x9csolventxe2x80x9d for the polymerization. It is preferred that the concentration of 1- and 2-butenes in the stream be as high as possible, since these are the preferred compounds to be polymerized. The butadiene content should be minimized because it may be a polymerization catalyst poison. The isobutene may have been previously removed for other uses. After being used in the polymerization (during which much or most of the 1-butene would have been polymerized), the butenes stream can be returned to the refinery for further processing.
In many of the these polymerizations certain general trends may be noted, although for all of these trends there are exceptions. These trends (and exceptions) can be gleaned from the Examples.
Pressure of the monomers (especially gaseous monomers such as ethylene) has an effect on the polymerizations in many instances. Higher pressure often affects the polymer microstructure by reducing branching, especially in ethylene containing polymers. This effect is more pronounced for Ni catalysts than Pd catalysts. Under certain conditions higher pressures also seem to give higher productivities and higher molecular weight. When an acrylate is present and a Pd catalyst is used, increasing pressure seems to decrease the acrylate content in the resulting copolymer.
Temperature also affects these polymerizations. Higher temperature usually increases branching with Ni catalysts, but often has little such effect using Pd catalysts. With Ni catalysts, higher temperatures appear to often decrease molecular weight. With Pd catalysts, when acrylates are present, increasing temperature usually increases the acrylate content of the polymer, but also often decreases the productivity and molecular weight of the polymer.
Anions surprisingly also often affect molecular weight of the polymer formed. More highly coordinating anions often give lower molecular weight polymers. Although all of the anions useful herein are relatively weakly coordinating, some are more strongly coordinating than others. The coordinating ability of such anions is known and has been discussed in the literature, see for instance W. Beck., et al., Chem. Rev., vol. 88 p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p. 927-942.(1993), both of which are hereby included by reference. The results found herein in which the molecular weight of the polymer produced is related to the coordinating ability of the anion used, is in line with the coordinating abilities of these anions as described in Beck (p. 1411) and Strauss (p. 932, Table II).
In addition to the xe2x80x9ctraditionalxe2x80x9d weakly coordinating anions cited in the paragraph immediately above, heterogeneous anions may also be employed. In these cases, the true nature of the counterion is poorly defined or unknown. Included in this group are MAO, MMAO and related aluminoxanes which do not form true solutions. The resulting counterions are thought to bear anionic aluminate moieties related to those cited in the paragraph immediately above. Polymeric anionic materials such as Nafion polyfluorosulfonic acid can function as non-coordinating counterions. In addition, a wide variety of heterogeneous inorganic materials can be made to function as non-coordinating counterions. Examples would include aluminas, silicas, silica/aluminas, cordierites, clays, MgCl2, and many others utilized as traditional supports for Ziegler-Natta olefin polymerization catalysts. These are generally materials which have Lewis or Bronsted acidity. High surface area is usually desired and often these materials will have been activated through some heating process. Heating may remove excess surface water and change the surface acidity from Bronsted to Lewis type. Materials which are not active in the role may often be made active by surface treatment. For instance, a surface-hydrated silica, zinc oxide or carbon can be treated with an organoaluminum compound to provide the required functionality.
The catalysts described herein can be heterogenized through a variety of means. The heterogeneous anions in the paragraph immediately above will all serve to heterogenize the catalysts. Catalysts can also be heterogenized by exposing them to small quantities of a monomer to encapsulate them in a polymeric material through which additional monomers will diffuse. Another method is to spray-dry the catalyst with its suitable non-coordinating counterion onto a polymeric support. Heterogeneous versions of the catalyst are particularly useful for running gas-phase polymerizations. The catalyst is suitably diluted and dispersed on the surface of the catalyst support to control the heat of polymerization. When applied to fluidized-bed polymerizations, the heterogeneous supports provide a convenient means of catalyst introduction.
Anions have been found to have another unexpected effect. They can effect the amount of incorporation of an acrylic monomer such as an ester into an olefin/acrylic copolymer. For instance it has been found that SbF6xe2x88x92 anion incorporates more fluorinated alkyl acrylate ester into an ethylene copolymer than BAF anion, see for instance Example 302.
Another item may effect the incorporation of polar monomers such as acrylic esters in olefin copolymers. It has been found that catalysts containing less bulky xcex1-diimines incorporate more of the polar monomer into the polymer (one obtains a polymer with a higher percentage of polar monomer) than a catalyst containing a more bulky xcex1-diimine, particularly when ethylene is the olefin comonomer. For instance, in an xcex1-diimine of formula (VIII), if R2 and R5 are 2,6-dimethylphenyl instead of 2,6-diisopropylphenyl, more acrylic monomer will be incorporated into the polymer. However, another common effect of using a less bulky catalyst is to produce a polymer with lower molecular weight. Therefore one may have to make a compromise between polar monomer content in the polymer and polymer molecular weight.
When an olefinic carboxylic acid is polymerized into the polymer, the polymer will of course contain carboxyl groups. Similarly in an ester containing polymer, some or all of the ester groups may be hydrolyzed to carboxyl groups (and vice versa). The carboxyl groups may be partially or completely converted into salts such as metallic salts. Such polymeric salts are termed ionomers. Ionomers are useful in adhesives, as ionomeric elastomers, and as molding resins. Salts may be made with ions of metals such as Na, K, Zn, Mg, Al, etc. The polymeric salts may be made by methods known to the artisan, for instance reaction of the carboxylic acid containing polymers with various compounds of the metals such as bases (hydroxides, carbonates, etc.) or other compounds, such as acetylacetonates. Novel polymers that contain carboxylic acid groups herein, also form novel ionomers when the carboxylic acid groups are partially or fully converted to carboxylate salts.
When copolymers of an olefinic carboxylic acid or olefinic ester and selected olefins are made, they may be crosslinked by various methods known in the art, depending on the specific monomers used to make the polymer. For instance, carboxyl or ester containing polymers may be crosslinked by reaction with diamines to form bisamides. Certain functional groups which may be present on the polymer may be induced to react to crosslink the polymer. For instance epoxy groups (which may be present as glycidyl esters) may be crosslinked by reaction of the epoxy groups, see for instance Example 135.
It has also been found that certain fluorinated olefins, some of them containing other functional groups may be polymerized by nickel and palladium catalysts. Not that these fluorinated olefins are included within the definition of H2Cxe2x95x90CHR17, wherein R17 can be considered to be substituted hydrocarbyl, the substitution being fluorine and possibly other substituents. Olefins which may be polymerized include H2Cxe2x95x90CH(CH2)aRfR42 wherein a is an integer of 2 to 20, Rf is perfluoroalkylene optionally containing one or more ether groups, and R42 is fluorine or a functional group. Suitable functional groups include hydrogen, chlorine, bromine or iodine, ester, sulfonic acid (xe2x80x94SO3H), and sulfonyl halide. Preferred groups for R42 include fluorine, ester, sulfonic acid, and sulfonyl fluoride. A sulfonic acid group containing monomer does not have to be polymerized directly. It is preferably made by hydrolysis of a sulfonyl halide group already present in an already made polymer. It is preferred that the perfluoroalkylene group contain 2 to 20 carbon atoms and preferred perfluoroalkylene groups are xe2x80x94(CF2)bxe2x80x94 wherein b is 2 to 20, and xe2x80x94(CF2)dOCF2CF2xe2x80x94 wherein d is 2 to 20. A preferred olefinic comonomer is ethylene or a linear xcex1-olefin, and ethylene is especially preferred. Polymerizations may be carried out with many of the catalysts described herein, see Examples 284 to 293.
As described herein, the resulting fluorinated polymers often don""t contain the expected amount of branching, and/or the lengths of the branches present are not those expected for a simple vinyl polymerization.
The resulting polymers may be useful for compatibilizing fluorinated and nonfluorinated polymers, for changing the surface characteristics of fluorinated or nonfluorinated polymers (by being mixed with them), as molding resins, etc. Those polymers containing functional groups may be useful where those functional groups may react or be catalysts. For instance, if a polymer is made with a sulfonyl fluoride group (R42 is sulfonyl fluoride) that group may be hydrolyzed to a sulfonic acid, which being highly fluorinated is well known to be a very strong acid. Thus the polymer may be used as an acid catalyst, for example for the polymerization of cyclic ethers such as tetrahydrofuran.
In this use it has been found that this polymer is more effective than a completely fluorinated sulfonic acid containing polymer. For such uses the sulfonic acid content need not be high, say only 1 to 20 mole percent, preferably about 2 to 10 mole percent of the repeat units in the polymer having sulfonic acid groups. The polymer may be crosslinked, in which case it may be soluble in the medium (for instance tetrahydrofuran), or it may be crosslinked so it swollen but not dissolved by the medium, Or it may be coated onto a substrate and optionally chemically attached and/or crosslinked, so it may easily be separated from the other process ingredients.
One of the monomers that may be polymerized by the above catalysts is ethylene (E), either by itself to form a homopolymer, or with xcex1-olefins and/or olefinic esters or carboxylic acids. The structure of the polymer may be unique in terms of several measurable properties.
These polymers, and others herein, can have unique structures in terms of the branching in the polymer. Branching may be determined by NMR spectroscopy (see the Examples for details), and this analysis can determine the total number of branches, and to some extent the length of the branches. Herein the amount of branching is expressed as the number of branches per 1000 of the total methylene (xe2x80x94CH2xe2x80x94) groups in the polymer, with one exception. Methylene groups that are in an ester grouping, i.e. xe2x80x94CO2R, are not counted as part of the 1000 methylenes. These methylene groups include those in the main chain and in the branches. These polymers, which are E homopolymers, have a branch content of about 80 to about 150 branches per 1000 methylene groups, preferably about 100 to about 130 branches per 1000 methylene groups. These branches do not include polymer end groups. In addition the distribution of the sizes (lengths) of the branches is unique. Of the above total branches, for every 100 that are methyl, about 30 to about 90 are ethyl, about 4 to about 20 are propyl, about 15 to about 50 butyl, about 3 to about 15 are amyl, and about 30 to about 140 are hexyl or longer, and it is preferred that for every 100 that are methyl, about 50 to about 75 are ethyl, about 5 to about 15 are propyl, about 24 to about 40 are butyl, about 5 to 10 are amyl, and about 65 to about 120 are hexyl or larger. These E homopolymers are often amorphous, although in some there may be a small amount of crystallinity.
Another polyolefin, which is an E homopolymer that can be made by these catalysts has about 20 to about 150 branches per 1000 methylene groups, and, per 100 methyl groups, about 4 to about 20 ethyl groups, about 1 to about 12 propyl groups, about 1 to about 12 butyl group, about 1 to about 10 amyl groups, and 0 to about 20 hexyl or larger groups. Preferably this polymer has about 40 to about 100 methyl groups per 1000 methylene groups, and per 100 methyl groups, about 6 to about 15 ethyl groups, about 2 to about 10 propyl groups, about 2 to about 10 butyl groups, about 2 to about 8 amyl groups, and about 2 to about 15 hexyl or larger groups.
Many of the polyolefins herein, including homopolyethylenes, may be crosslinked by various methods known in the art, for instance by the use of peroxide or other radical generating species which can crosslink these polymers. Such crosslinked polymers are novel when the uncrosslinked polymers from which they are derived are novel, because for the most part the structural feature(s) of the uncrosslinked polymers which make them novel will be carried over into the crosslinked forms.
In addition, some of the E homopolymers have an exceptionally low density, less than about 0.86 g/mL, preferably about 0.85 g/mL or less, measured at 25xc2x0 C. This density is based on solid polymer.
Homopolymers of polypropylene (P) can also have unusual structures. Similar effects have been observed with other xcex1-olefins (e.g. 1-hexene). A xe2x80x9cnormalxe2x80x9d P homopolymer will have one methyl group for each methylene group (or 1000 methyl groups per 1000 methylene groups), since the normal repeat unit is xe2x80x94CH(CH3)CH2xe2x80x94. However, using a catalyst of formula (I) in which M is Ni(II) in combination with an alkyl aluminum compound it is possible to produce a P homopolymer with about 400 to about 600 methyl groups per 1000 methylene groups, preferably about 450 to about 550 methyl groups per 1000 methylene groups. Similar effects have been observed with other xcex1-olefins (e.g. 1-hexene)
In the polymerization processes described herein olefinic esters and/or carboxylic acids may also be present, and of course become part of the copolymer formed. These esters may be copolymerized with one or more of E and one or more xcex1-olefins. When copolymerized with E alone polymers with unique structures may be formed.
In many such E/olefinic ester and/or carboxylic acid copolymers the overall branching level and the distribution of branches of various sizes are unusual. In addition, where and how the esters or carboxylic acids occur in the polymer is also unusual. A relatively high proportion of the repeat units derived from the olefinic esters are at the ends of branches. In such copolymers, it is preferred that the repeat units derived from the olefinic esters and carboxylic acids are about 0.1 to 40 mole percent of the total repeat units, more preferably about 1 to about 20 mole percent. In a preferred ester, m is 0 and R1 is hydrocarbyl or substituted hydrocarbyl. It is preferred that R1 is alkyl containing 1 to 220 carbon atoms, more preferred that it contains 1 to 4 carbon atoms, and especially preferred that R1 is methyl.
One such preferred dipolymer has about 60 to 100 methyl groups (excluding methyl groups which are esters) per 1000 methylene groups in the polymer, and contains, per 100 methyl branches, about 45 to about 65 ethyl branches, about 1 to about 3 propyl branches, about 3 to about 10 butyl branches, about 1 to about 3 amyl branches, and about 15 to about 25 hexyl or longer branches. In addition, the ester and carboxylic acid containing repeat units are often distributed mostly at the ends of the branches as follows. If the branches, and the carbon atom to which they are attached to the main chain, are of the formula xe2x80x94CH(CH2)nCO2R1, wherein the CH is part of the main chain, then in some of these polymers about 40 to about 50 mole percent of ester groups are found in branches where n is 5 or more, about 10 to about 20 mole percent when n is 4, about 20 to 30 mole percent when n is 1, 2 and 3 and about 5 to about 15 mole percent when n is 0. When n is 0, an acrylate ester has polymerized xe2x80x9cnormallyxe2x80x9d as part of the main chain, with the repeat unit xe2x80x94CH2xe2x80x94CHCO2R1xe2x80x94.
These branched polymers which contain olefin and olefinic ester monomer units, particularly copolymers of ethylene and methyl acrylate and/or other acrylic esters are particularly useful as viscosity modifiers for lubricating oils, particularly automotive lubricating oils.
Under certain polymerization conditions, some of the polymerization catalysts described herein produce polymers whose structure is unusual, especially considering from what compounds (monomers) the polymers were made, and the fact that polymerization catalysts used herein are so-called transition metal coordination catalysts (more than one compound may be involved in the catalyst system, one of which must include a transition metal). Some of these polymers were described in a somewhat different way above, and they may be described as xe2x80x9cpolyolefinsxe2x80x9d even though they may contain other monomer units which are not olefins (e.g., olefinic esters). In the polymerization of an unsaturated compound of the formula H2Cxe2x95x90CH(CH2)eG, wherein e is 0 or an integer of 1 or more, and G is hydrogen or xe2x80x94CO2R1, the usual (xe2x80x9cnormalxe2x80x9d) polymeric repeat unit obtained would be xe2x80x94CH2xe2x80x94CH[(CH2)eG]xe2x80x94, wherein the branch has the formula xe2x80x94(CH2)eG. However, with some of the instant catalysts a polymeric unit may be xe2x80x94CH2xe2x80x94CH[(CH2)fG]xe2x80x94, wherein fxe2x89xa0e, and f is 0 or an integer of 1 or more. If f less than e, the xe2x80x9cextraxe2x80x9d methylene groups may be part of the main polymer chain. If fxe2x89xa0e (parts of) additional monomer molecules may be incorporated into that branch. In other words, the structure of any polymeric unit may be irregular and different for monomer molecules incorporated into the polymer, and the structure of such a polymeric unit obtained could be rationalized as the result of xe2x80x9cmigration of the active polymerizing sitexe2x80x9d up and down the polymer chain, although this may not be the actual mechanism. This is highly unusual, particularly for polymerizations employing transition metal coordination catalysts.
For xe2x80x9cnormalxe2x80x9d polymerizations, wherein the polymeric unit xe2x80x94CH2xe2x80x94CH[(CH2)eG]xe2x80x94 is obtained, the theoretical amount of branching, as measured by the number of branches per 1000 methylene (xe2x80x94CH2xe2x80x94) groups can be calculated as follows which defines terms xe2x80x9ctheoretical branchesxe2x80x9d or xe2x80x9ctheoretical branchingxe2x80x9d herein:       Theoretical    ⁢          xe2x80x83        ⁢    branches    =            1000      *      Total      ⁢              xe2x80x83            ⁢      mole      ⁢              xe2x80x83            ⁢      fraction      ⁢              xe2x80x83            ⁢      of      ⁢              xe2x80x83            ⁢      α      ⁢              -            ⁢      olefins                                            {                                          [                                  ∑                                      (                                                                  2                        *                        mole                        ⁢                                                  xe2x80x83                                                ⁢                        fraction                        ⁢                                                  xe2x80x83                                                ⁢                        e                                            =                      0                                        )                                                  ]                            +                                                                                      [                              ∑                                  (                                      mole                    ⁢                                          xe2x80x83                                        ⁢                    fraction                    ⁢                                          xe2x80x83                                        ⁢                    α                    ⁢                                          -                                        ⁢                    olefin                    *                    e                                    )                                            ]                        }                              
In this equation, an xcex1-olefin is any olefinic compound H2Cxe2x95x90CH(CH2)eG wherein exe2x89xa00. Ethylene or an acrylic compound are the cases wherein e=0. Thus to calculate the number of theoretical branches in a polymer made from 50 mole percent ethylene (e=0), 30 mole percent propylene (e=1) and 20 mole percent methyl 5-heptenoate (e=4) would be as follows:                               Theoretical          ⁢                      xe2x80x83                    ⁢          branches                =                              1000            *            0.5                                {                                          [                                  (                                      2                    *                    0.5                                    )                                ]                            +                              [                                                      (                                          0.30                      *                      1                                        )                                    +                                      (                                          0.20                      *                      4                                        )                                                  ]                                      }                                                  =                  238          ⁢                      xe2x80x83                    ⁢                                    (                              branches                ⁢                                  /                                ⁢                1000                ⁢                                  xe2x80x83                                ⁢                methylenes                            )                        .                              
The xe2x80x9c1000 methylenesxe2x80x9d include all of the methylene groups in the polymer, including methylene groups in the branches.
For some of the polymerizations described herein, the actual amount of branching present in the polymer is considerably greater than or less than the above theoretical branching calculations would indicate. For instance, when an ethylene homopolymer is made, there should be no branches, yet there are often many such branches. When an xcex1-olefin is polymerized, the branching level may be much lower or higher than the theoretical branching level. It is preferred that the actual branching level is at 90% or less of the theoretical branching level, more preferably about 80% or less of the theoretical branching level, or 110% or more of the theoretical branching level, more preferably about 120% or more of the theoretical branching level. The polymer should also have at least about 50 branches per 1000 methylene units, preferably about 75 branches per 1000 methylene units, and more preferably about 100 branches per 1000 methylene units. In cases where there are xe2x80x9c0xe2x80x9d branches theoretically present, as in ethylene homopolymers or copolymers with acrylics, excess branches as a percentage cannot be calculated. In that instance if the polymer has 50 or more, preferably 75 or more branches per 1000 methylene groups, it has excess branches (i.e. in branches in which f greater than 0).
These polymers also have xe2x80x9cat least two branches of different lengths containing less than 6 carbon atoms each.xe2x80x9d By this is meant that branches of at least two different lengths (i.e. number of carbon atoms), and containing less than 6 carbon atoms, are present in the polymer. For instance the polymer may contain ethyl and butyl branches, or methyl and amyl branches.
As will be understood from the above discussion, the lengths of the branches (xe2x80x9cfxe2x80x9d) do not necessarily correspond to the original sizes of the monomers used (xe2x80x9cexe2x80x9d). Indeed branch lengths are often present which do not correspond to the sizes of any of the monomers used and/or a branch length may be present xe2x80x9cin excessxe2x80x9d. By xe2x80x9cin excessxe2x80x9d is meant there are more branches of a particular length present than there were monomers which corresponded to that branch length in the polymer. For instance, in the copolymerization of 75 mole percent ethylene and 25 mole percent 1-butene it would be expected that there would be 125 ethyl branches per 1000 methylene carbon atoms. If there were more ethyl branches than that, they would be in excess compared to the theoretical branching. There may also be a deficit of specific length branches. If there were less than 125 ethyl branches per 1000 methylene groups in this polymer there would be a deficit. Preferred polymers have 90% or less or 110% or more of the theoretical amount of any branch length present in the polymer, and it is especially preferred if these branches are about 80% or less or about 120% or more of the theoretical amount of any branch length. In the case of the 75 mole percent ethylene/25 mole percent 1-butene polymer, the 90% would be about 113 ethyl branches or less, while the 110% would be about 138 ethyl branches or more. Such polymers may also or exclusively contain at least 50 branches per 1000 methylene atoms with lengths which should not theoretically (as described above) be present at all.
These polymers also have xe2x80x9cat least two branches of different lengths containing less than 6 carbon atoms each.xe2x80x9d By this is meant that branches of at least two different lengths (i.e. number of carbon atoms), and containing less than 6 carbon atoms, are present in the polymer. For instance the polymer may contain ethyl and butyl branches, or methyl and amyl branches.
Some of the polymers produced herein are novel because of unusual structural features. Normally, in polymers of alpha-olefins of the formula CH2xe2x95x90CH(CH2)aH wherein a is an integer of 2 or more made by coordination polymerization, the most abundant, and often the only, branches present in such polymers have the structure xe2x80x94(CH2)aH. Some of the polymers produced herein are novel because methyl branches comprise about 25% to about 75% of the total branches in the polymer. Such polymers are described in Examples 139, 162, 173 and 243-245. Some of the polymers produced herein are novel because in addition to having a high percentage (25-75%) of methyl branches (of the total branches present), they also contain linear branches of the structure (CH2)nH wherein n is an integer of six or greater. Such polymers are described in Examples 139, 173 and 243-245. Some of the polymers produced herein are novel because in addition to having a high percentage (25-75%) of methyl branches (of the total branches present), they also contain the structure (XXVI), preferably in amounts greater than can be accounted for by end groups, and more preferably greater than 0.5 (XXVI) groups per thousand methyl groups in the polymer greater than can be accounted for by end groups. 
Normally, homo- and copolymers of one or more alpha-olefins of the formula CH2xe2x95x90CH(CH2)aH wherein a is an integer of 2 or more contain as part of the polymer backbone the structure (XXV) 
wherein R35 and R36 are alkyl groups. In most such polymers of alpha-olefins of this formula (especially those produced by coordination-type polymerizations), both of R35 and R36 are xe2x80x94(CH2)aH. However, in certain of these polymers described herein, about 2 mole percent or more, preferably about 5 mole percent or more and more preferably about 50 mole percent or more of the total amount of (XXV) in said polymer consists of the structure where one of R35 and R36 is a methyl group and the other is an alkyl group containing two or more carbon atoms. Furthermore, in certain of these polymers described herein, structure (XXV) may occur in side chains as well as in the polymer backbone. Structure (XXV) can be detected by 13C NMR. The signal for the carbon atom of the methylene group between the two methine carbons in (XXV) usually occurs in the 13C NMR at 41.9 to 44.0 ppm when one of R35 and R36 is a methyl group and the other is an alkyl group containing two or more carbon atoms, while when both R35 and R36 contain 2 or more carbon atoms, the signal for the methylene carbon atom occurs at 39.5 to 41.9 ppm. Integration provides the relative amounts of these structures present in the polymer. If there are interfering signals from other carbon atoms in these regions, they must be subtracted from the total integrals to give correct values for structure (XXV).
Normally, homo- and copolymers of one or more alpha-olefins of the formula CH2xe2x95x90CH(CH2)aH wherein a is an integer of 2 or more (especially those made by coordination polymerization) contain as part of the polymer backbone structure (XXIV) wherein n is 0, 1, or 2. When n is 0, this structure is termed xe2x80x9chead to headxe2x80x9d polymerization. When n is 1, this structure is termed xe2x80x9chead to tailxe2x80x9d polymerization. When n is 2, this structure is termed xe2x80x9ctail to tailxe2x80x9d polymerization. In most such polymers of alpha-olefins of this formula (especially those produced by coordination-type polymerizations), both of R37 and R38 are xe2x80x94(CH2)aH. However some of the polymers of alpha-olefins of this formula described herein are novel in that they also contain structure (XXIV) wherein nxe2x95x90a, R37 is a methyl group, and R38 is an alkyl group with 2 or more carbon atoms. 
Normally polyethylene made by coordination polymerization has a linear backbone with either no branching, or small amounts of linear branches. Some of the polyethylenes described herein are unusual in that they contain structure (XXVII) which has a methine carbon that is not part of the main polymer backbone. 
Normally, polypropylene made by coordination polymerization has methyl branches and few if any branches of other sizes. Some of the polypropylenes described herein are unusual in that they contain one or both of the structures (XXVIII) and (XXIX). 
As the artisan understands, in coordination polymerization alpha-olefins of the formula CH2xe2x95x90CH(CH2)aH may insert into the growing polymer chain in a 1,2 or 2,1 manner. Normally these insertion steps lead to 1,2-enchainment or 2,1-enchainment of the monomer. Both of these fundamental steps form a xe2x80x94(CH2)aH branch. However, with some catalysts herein, some of the initial product of 1,2 insertion can rearrange by migration of the coordinated metal atom to the end of the last inserted monomer before insertion of additional monomer occurs. This results in omega, 2-enchainment and the formation of a methyl branch. 
It is also known that with certain other catalysts, some of the initial product of 2,1 insertion can rearrange in a similar manner by migration of the coordinated metal atom to the end of the last inserted monomer. This results in omega, 1-enchainment and no branch is formed. 
Of the four types of alpha-olefin enchainment, omega, 1-enchainment is unique in that it does not generate a branch. In a polymer made from an alpha-olefin of the formula CH2xe2x95x90CH(CH2)aH, the total number of branches per 1000 methylene groups (B) can be expressed as:
B=(1000) (1xe2x88x92Xxcfx89,1)/[(1xe2x88x92Xxcfx89,1)a+Xxcfx89,1(a+2)]
where Xxcfx89,1 is the fraction of omega, 1-enchainment
Solving this expression for Xxcfx89,1 gives:
Xxcfx89,1=(1000xe2x88x92aB)/(1000+2B)
This equation provides a means of calculating the fraction of omega, 1-enchainment in a polymer of a linear alpha-olefin from the total branching B. Total branching can be measured by 1H NMR or 13C NMR. Similar equations can be written for branched alpha-olefins. For example, the equation for 4-methyl-1-pentene is:
Xxcfx89,1=(2000xe2x88x922B)/(1000+2B)
Most polymers of alpha-olefins made by other coordination polymerization methods have less than 5% omega, 1-enchainment. Some of the alpha-olefin polymers described herein have unusually large amounts (say  greater than 5%) of omega, 1-enchainment. In essence this is similar to stating that a polymer made from an xcex1-olefin has much less than the xe2x80x9cexpectedxe2x80x9d amount of branching. Although many of the polymerizations described herein give substantial amounts of xcfx89,1- and other unusual forms of enchainment of olefinic monomers, it has surprisingly been found that xe2x80x9cunsymmetricalxe2x80x9d xcex1-diimine ligands of formula (VIII) give especially high amounts of xcfx89,1-enchainment. In particular when R2 and R5 are phenyl, and one or both of these is substituted in such a way as different sized groups are present in the 2 and 6 position of the phenyl ring(s), xcfx89,1-enchainment is enhanced. For instance, if one or both of R2 and R5 are 2-t-butylphenyl, this enchainment is enhanced. In this context when R2 and/or R5 are xe2x80x9csubstitutedxe2x80x9d phenyl the substitution may be not only in the 2 and/or 6 positions, but on any other position in the phenyl ring. For instance, 2,5-di-t-butylphenyl, and 2-t-butyl-4,6-dichlorophenyl would be included in substituted phenyl.
The steric effect of various groupings has been quantified by a parameter called Es, see R. W. Taft, Jr., J. Am. Chem. Soc., vol. 74, p. 3120-3128, and M. S. Newman, Steric Effects in Organic Chemistry, John Wiley and Sons, New York, 1956, p. 598-603. For the purposes herein, the Es values are those for o-substituted benzoates described in these publications. If the value for Es for any particular group is not known, it can be determined by methods described in these publications. For the purposes herein, the value of hydrogen is defined to be the same as for methyl. It is preferred that difference in Es, when R2 (and preferably also R5) is phenyl, between the groups substituted in the 2 and 6 positions of the phenyl ring is at least 0.15, more preferably at least about 0.20, and especially preferably about 0.6 or more. These phenyl groups may be unsubstituted or substituted in any other manner in the 3, 4 or 5 positions.
These differences in Es are preferred in a diimine such as (VIII), and in any of the polymerization processes herein wherein a metal complex containing an xcex1-diimine ligand is used or formed. The synthesis and use of such xcex1-diimines is illustrated in Examples 454-463.
Because of the relatively large amounts of xcfx89,1-enchainment that may be obtained using some of the polymerization catalysts reported herein novel polymers can be made. Among these homopolypropylene (PP). In some of the PP""s made herein the structure 
may be found. In this structure each Ca is a methine carbon atom that is a branch point, while each Cb is a methylene group that is more than 3 carbon atoms removed from any branch point (Ca). Herein methylene groups of the type xe2x80x94CbH2xe2x80x94 are termed xcex4+ (or delta+) methylene groups. Methylene groups of the type xe2x80x94CdH2xe2x80x94, which are exactly the third carbon atom from a branch point, are termed xcex3 (gamma) methylene groups. The NMR signal for the 8+methylene groups occurs at about 29.75 ppm, while the NMR signal for the xcex3 methylene groups appears at about 30.15 ppm. Ratios of these types of methylene groups to each other and the total number of methylene groups in the PP is done by the usual NMR integration techniques.
It is preferred that PP""s made herein have about 25 to about 300 xcex4+methylene groups per 1000 methylene groups (total) in the PP.
It is also preferred that the ratio of xcex4+:xcex3 methylene groups in the PP be 0.7 to about 2.0.
The above ratios involving xcex4+ and xcex3 methylene groups in PP are of course due to the fact that high relatively high xcfx89,1 enchainment can be obtained. It is preferred that about 30 to 60 mole percent of the monomer units in PP be enchained in an xcfx89,1 fashion. Using the above equation, the percent xcfx89,1 enchainment for polypropylene can be calculated as:
% xcfx89,1=(100) (1000xe2x88x92B)/(1000+2B)
wherein B is the total branching (number of methyl groups) per 1000 methylene groups in the polymer.
Homo- or copolymers of one or more linear xcex1-olefins containing 3 to 8 carbon atoms may also have xcex4+ carbon atoms in them, preferably at least about 1 or more xcex4+ carbon atoms per 1000 methylene groups.
The above polymerization processes can of course be used to make relatively random copolymers (except for certain CO copolymers) of various possible monomers. However, some of them can also be used to make block polymers. A block polymer is conventionally defined as a polymer comprising molecules in which there is a linear arrangement of blocks, a block being a portion of a polymer molecule which the monomeric units have at least one constitutional or configurational feature absent from adjacent portions (definition from H. Mark, et al., Ed., Encyclopedia of Polymer Science and Engineering, Vol. 2, John Wiley and Sons, New York, 1985, p. 324). Herein in a block copolymer, the constitutional difference is a difference in monomer units used to make that block, while in a block homopolymer the same monomer(s) are used but the repeat units making up different blocks are different structure and/or ratios of types of structures.
Since it is believed that many of the polymerization processes herein have characteristics that often resemble those of living polymerizations, making block polymers may be relatively easy. One method is to simply allow monomer(s) that are being polymerized to be depleted to a low level, and then adding different monomer(s) or the same combination of monomers in different ratios. This process may be repeated to obtain polymers with many blocks.
Lower temperatures, say about less than 0xc2x0 C., preferably about xe2x88x9210xc2x0 to about xe2x88x9230xc2x0, tends to enhance the livingness of the polymerizations. Under these conditions narrow molecular weight distribution polymers may be obtained (see Examples 367-369 and 371), and block copolymers may also be made (Example 370).
As pointed out above, certain polymerization conditions, such as pressure, affect the microstructure of many polymers. The microstructure in turn affects many polymer properties, such as crystallization. Thus, by changing polymerization conditions, such as the pressure, one can change the microstructure of the part of the polymer made under those conditions. This of course leads to a block polymer, a polymer have defined portions having structures different from other defined portions. This may be done with more than one monomer to obtain a block copolymer, or may be done with a single monomer or single mixture of monomers to obtain a block homopolymer. For instance, in the polymerization of ethylene, high pressure sometimes leads to crystalline polymers, while lower pressures give amorphous polymers. Changing the pressure repeatedly could lead to an ethylene homopolymer containing blocks of amorphous polyethylene and blocks of crystalline polyethylene. If the blocks were of the correct size, and there were enough of them, a thermoplastic elastomeric homopolyethylene could be produced. Similar polymers could possibly be made from other monomer(s), such as propylene.
Homopolymers of xcex1-olefins such as propylene, that is polymers which were made from a monomer that consisted essentially of a single monomer such as propylene, which are made herein, sometimes exhibit unusual properties compared to their xe2x80x9cnormalxe2x80x9d homopolymers. For instance, such a homopolypropylene usually would have about 1000 methyl groups per 1000 methylene groups. Polypropylenes made herein typically have about half that many methyl groups, and in addition have some longer chain branches. Other xcex1-olefins often give polymers whose microstructure is analogous to these polypropylenes when the above catalysts are used for the polymerization.
These polypropylenes often exhibit exceptionally low glass transition temperatures (Tg""s). xe2x80x9cNormalxe2x80x9d polypropylene has a Tg of about xe2x88x9217xc2x0 C., but the polypropylenes herein have a Tg of xe2x88x9230xc2x0 C. or less, preferably about xe2x88x9235xc2x0 C. or less, and more preferably about xe2x88x9240xc2x0 C. or less. These Tg""s are measured by Differential Scanning Calorimetry at a heating rate of 10xc2x0 C./min, and the Tg is taken as the midpoint of the transition. These polypropylenes preferably have at least 50 branches (methyl groups) per 1000 carbon atoms, more preferably at least about 100 branches per 1000 methylene groups.
Previously, when cyclopentene was coordination polymerized to higher molecular weights, the resulting polymer was essentially intractable because of its very high melting point, greatly above 300xc2x0 C. Using the catalysts here to homopolymerize cyclopentene results in a polymer that is tractable, i.e., may be reformed, as by melt forming. Such polymers have an end of melting point of about 320xc2x0 C. or less, preferably about 300xc2x0 C. or less, or a melting point of about 275xc2x0 C. or less, preferably about 250xc2x0 C. or less. The melting point is determined by Differential Scanning Calorimetry at a heating rate of 15xc2x0 C./min, and taking the maximum of the melting endotherm as the melting point. However these polymers tend to have relatively diffuse melting points, so it is preferred to measure the xe2x80x9cmelting pointxe2x80x9d by the end of melting point. The method is the same, except the end of melting is taken as the end (high temperature end) of the melting endotherm which is taken as the point at which the DSC signal returns to the original (extrapolated) baseline. Such polymers have an average degree of polymerization (average number of cyclopentene repeat units per polymer chain) of about 10 or more, preferably about 30 or more, and more preferably about 50 or more.
In these polymers, enchainment of the cyclopentene repeat units is usually as cis-1,3-pentylene units, in contrast to many prior art cyclopentenes which were enchained as 1,2-cyclopentylene units. It is preferred that about 90 mole percent or more, more preferably about 95 mole percent or more of the enchained cyclopentene units be enchained as 1,3-cyclopentylene units, which are preferably cis-1,3-cyclopentylene units.
The X-ray powder diffraction pattern of the instant poly(cyclopentenes) is also unique. To produce cyclopentene polymer samples of uniform thickness for X-ray measurements, powder samples were compressed into disks approximately 1 mm thick and 32 mm in diameter. X-ray powder diffraction patterns of the samples were collected over the range 10-50xc2x0 2xcex8. The diffraction data were collected using an automated Philips xcex8-xcex8diffractometer (Philips X""pert System) operating in the symmetrical transmission mode (Ni-filtered CuKa radiation, equipped with a diffracted beam collimator (Philips Thin Film Collimator system), Xe filled proportional detector, fixed step mode (0.05xc2x0/step), 12.5 sec./step, 1/40xc2x0 divergence slit). Reflection positions were identified using the peak finding routine in the APD suite of programs provided with the X""pert System. The X-ray powder diffraction pattern had reflections at approximately 17.3xc2x0, 19.3xc2x0, 24.2xc2x0, and 40.7xc2x0 2xcex8, which correspond to d-spacings of approximately 0.512, 0.460, 0.368 and 0.222 nm, respectively. These polymers have a monoclinic unit cell of the approximate dimensions: a=0.561 nm; b=0.607 nm; c=7.37 nm; and g=123.2xc2x0.
Copolymers of cyclopentene and various other olefins may also be made. For instance copolymer of ethylene and cyclopentene may also be made. In such a copolymer it is preferred that at least 50 mole percent, more preferably at least about 70 mole percent, of the repeat units are derived from cyclopentene. As also noted above, many of the polymerization systems described herein produce polyethylenes that have considerable branching in them. Likewise the ethylene units which are copolymerized with the cyclopentene herein may also be branched, so it is preferred that there be at least 20 branches per 1000 methylene carbon atoms in such copolymers. In this instance, the xe2x80x9cmethylene carbon atomsxe2x80x9d referred to in the previous sentence do not include methylene groups in the cyclopentene rings. Rather it includes methylene groups only derived from ethylene or other olefin, but not cyclopentene.
Another copolymer that may be prepared is one from cyclopentene and an xcex1-olefin, more preferably a linear xcex1-olefin. It is preferred in such copolymers that repeat units derived from cyclopentene are 50 mole percent or more of the repeat units. As mentioned above, xcex1-olefins may be enchained in a 1,xcfx89 fashion, and it is preferred that at least 10 mole percent of the repeat units derived from the xcex1-olefin be enchained in such a fashion. Ethylene may also be copolymerized with the cyclopentene and xcex1-olefin.
Poly(cyclopentene) and copolymers of cyclopentene, especially those that are (semi)crystalline, may be used as molding and extrusion resins. They may contain various materials normally found in resins, such as fillers, reinforcing agents, antioxidants, antiozonants, pigments, tougheners, compatibilizers, dyes, flame retardant, and the like. These polymers may also be drawn or melt spun into fibers. Suitable tougheners and compatibilizers include polycyclopentene resin which has been grafted with maleic anhydride, an grafted EPDM rubber, a grafted EP rubber, a functionalized styrene/butadiene rubber, or other rubber which has been modified to selectively bond to components of the two phases.
In all of the above homo- and copolymers of cyclopentene, where appropriate, any of the preferred state may be combined any other preferred state(s).
The homo- and copolymers of cyclopentene described above may used or made into certain forms as described below:
1. The cyclopentene polymers described above may be part of a polymer blend. That is they may be mixed in any proportion with one or more other polymers which may be thermoplastics and/or elastomers. Suitable polymers for blends are listed below in the listing for blends of other polymers described herein. One preferred type of polymer which may be blended is a toughening agent or compatibilizer, which is often elastomeric and/or contains functional groups which may help compatibilize the mixture, such as epoxy or carboxyl.
2. The polycyclopentenes described herein are useful in a nonwoven fabric comprising fibrillated three-dimensional network fibers prepared by using of a polycyclopentene resin as the principal component. It can be made by flash-spinning a homogeneous solution containing a polycyclopentene. The resultant nonwoven fabric is excellent in heat resistance, dimensional stability and solvent resistance.
3. A shaped part of any of the cyclopentene containing resins. This part may be formed by injection molding, extrusion, and thermoforming. Exemplary uses include molded part for automotive use, medical treatment container, microwave-range container, food package container such as hot packing container, oven container, retort container, etc., and heat-resisting transparent container such as heat-resisting bottle.
4. A sheet or film of any of the cyclopentene containing resins. This sheet or film may be clear and may be used for optical purposes (i.e. breakage resistant glazing). The sheet or film may be oriented or unoriented. Orientation may be carried out by any of the known methods such a uniaxial or biaxial drawing. The sheet or film may be stampable or thermoformable.
5. The polycyclopentene resins are useful in nonwoven fabrics or microfibers which are produced by melt-blowing a material containing as a main component a polycyclopentene. A melt-blowing process for producing a fabric or fiber comprises supplying a polycyclopentene in a molten form from at least one orifice of a nozzle into a gas stream which attenuates the molten polymer into microfibers. The nonwoven fabrics are excellent in heat-resistant and chemical resistant characteristics, and are suitable for use as medical fabrics, industrial filters, battery separators and so forth. The microfibers are particularly useful in the field of high temperature filtration, coalescing and insulation.
6. A laminate in which one or more of the layers comprises a cyclopentene resin. The laminate may also contain adhesives, and other polymers in some or all of the layers, or other materials such as paper, metal foil, etc. Some or all of the layers, may be oriented in the same or different directions. The laminate as a whole may also be oriented. Such materials are useful for containers, or other uses where barrier properties are required.
7. A fiber of a cyclopentene polymer. This fiber may be undrawn or drawn to further orient it. It is useful for apparel and in industrial application where heat resistance and/or chemical resistance are important.
8. A foam or foamed object of a cyclopentene polymer. The foam may be formed in any conventional manner such as by using blowing agents.
9. The cyclopentene resins may be microporous membranes. They may be used in process wherein semi-permeable membranes are normally used.
In addition, the cyclopentene resins may be treated or mixed with other materials to improve certain properties, as follows:
1. They may further be irradiated with electron rays. This often improves heat resistance and/or chemical resistance, and is relatively inexpensive. Thus the molding is useful as a material required to have high heat resistance, such as a structural material, a food container material, a food wrapping material or an electric or electronic part material, particularly as an electric or electronic part material, because it is excellent in soldering resistance.
2. Parts with a crystallinity of at least 20% may be obtained by subjecting cyclopentene polymers having an end of melting point between 240 and 300xc2x0 C. to heat treatment (annealing) at a temperature of 120xc2x0 C. to just below the melting point of the polymer. Preferred conditions are a temperature of 150 to 280xc2x0 C. for a period of time of 20 seconds to 90 minutes, preferably to give a cyclopentene polymer which has a heat deformation temperature of from 200 to 260xc2x0 C. These parts have good physical properties such as heat resistance and chemical resistance, and thus are useful for, for example, general construction materials, electric or electronic devices, and car parts.
3. Cyclopentene resins may be nucleated to promote crystallization during processing. An example would be a polycyclopentene resin composition containing as main components (A) 100 parts by weight of a polycyclopentene and (B) 0.01 to 25 parts by weight of one or more nucleating agents selected from the group consisting of (1) metal salts of organic acids, (2) inorganic compounds, (3) organophosphorus compounds, and/or (4) metal salts of ionic hydrocarbon copolymer. Suitable nucleating agents may be sodium methylenebis(2,4-di-tertbutylphenyl) acid phosphate, sodium bis(4-tert-butylphenyl) phosphate, aluminum p-(tert-butyl) benzoate, talc, mica, or related species. These could be used in a process for producing polycyclopentene resin moldings by molding the above polycyclopentene resin composition at a temperature above their melting point.
4. Flame retardants and flame retardant combinations may be added to a cyclopentene polymer. Suitable flame retardants include a halogen-based or phosphorus-based flame retardant, antimony trioxide, antimony pentoxide, sodium antimonate, metallic antimony, antimony trichloride, antimony pentachloride, antimony trisulfide, antimony pentasulfide, zinc borate, barium metaborate or zirconium oxide. They may be used in conventional amounts.
5. An oxidants may be used in conventional amounts to improve the stability of the cyclopentene polymers. For instance 0.005 to 30 parts by weight, per 100 parts by weight of the cyclopentene polymer, of an antioxidant selected from the group consisting of a phosphorous containing antioxidant, a phenolic antioxidant or a combination thereof. The phosphorous containing antioxidant may be a monophosphite or diphosphite or mixture thereof and the phenolic antioxidant may be a dialkyl phenol, trialkyl phenol, diphenylmonoalkoxylphenol, a tetraalkyl phenol, or a mixture thereof. A sulfur-containing antioxidant may also be used alone or in combination with other antioxidants.
6. Various fillers or reinforcers, such as particulate or fibrous materials, may be added to improve various physical properties.
7. xe2x80x9cSpecialxe2x80x9d physical properties can be obtained by the use of specific types of materials. Electrically conductive materials such as fine metallic wires or graphite may be used to render the polymer electrically conductive. The temperature coefficient of expansion may be regulated by the use of appropriate fillers, and it may be possible to even obtain materials with positive coefficients of expansion. Such materials are particularly useful in electrical and electronic parts.
8. The polymer may be crosslinked by irradiation or chemically as by using peroxides, optionally in the presence of suitable coagents. Suitable peroxides include benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl peroxide, tert-butylperoxybenzoate, tert-butylcumyl peroxide, tert-butylhydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,1,1-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, 2,2-bis(tert-butylperoxy)butane and tert-butylperoxybenzene.
When polymerizing cyclopentene, it has been found that some of the impurities that may be found in cyclopentene poison or otherwise interfere with the polymerizations described herein. Compounds such as 1,3-pentadiene (which can be removed by passage through 5A molecular sieves), cyclopentadiene (which can be removed by distillation from Na), and methylenecyclobutane (which can be removed by distillation from polyphosphoric acid), may interfere with the polymerization, and their level should be kept as low as practically possible.
The above polymers (in general) are useful in many applications. Crystalline high molecular weight polymers are useful as molding resins, and for films for use in packaging. Amorphous resins are useful as elastomers, and may be crosslinked by known methods, such as by using free radicals. When such amorphous resins contain repeat units derived from polar monomers they are oil resistant. Lower molecular weight polymers are useful as oils, such as in polymer processing aids. When they contain polar groups, particularly carboxyl groups, they are useful in adhesives.
In many of the above polymerizations, the transition metal compounds employed as (part of the) catalysts contain(s) (a) metal atom(s) in a positive oxidation state. In addition, these complexes may have a square planar configuration about the metal, and the metal, particularly nickel or palladium, may have a d8 electronic configuration. Thus some of these catalysts may be said to have a metal atom which is cationic and has a d8-square planar configuration.
In addition these catalysts may have a bidentate ligand wherein coordination to the transition metal is through two different nitrogen atoms or through a nitrogen atom and a phosphorus atom, these nitrogen and phosphorus atoms being part of the bidentate ligand. It is believed that some of these compounds herein are effective polymerization catalysts at least partly because the bidentate ligands have sufficient steric bulk on both sides of the coordination plane (of the square planar complex). Some of the Examples herein with the various catalysts of this type illustrate the degree of steric bulk which may be needed for such catalysts. If such a complex contains a bidentate ligand which has the appropriate steric bulk, it is believed that it produces polyethylene with a degree of polymerization of at least about 10 or more.
It is also believed that the polymerization catalysts herein are effective because unpolymerized olefinic monomer can only slowly displace from the complex a coordinated olefin which may be formed by xcex2-hydride elimination from the growing polymer chain which is attached to the transition metal. The displacement can occur by associative exchange. Increasing the steric bulk of the ligand slows the rate of associative exchange and allows polymer chain growth. A quantitative measure of the steric bulk of the bidentate ligand can be obtained by measuring at xe2x88x9285xc2x0 C. the rate of exchange of free ethylene with complexed ethylene in a complex of formula (XI) as shown in equation 1 using standard 1H NMR techniques, which is called herein the Ethylene Exchange Rate (EER). The neutral bidentate ligand is represented by YN where Y is either N or P. The EER is measured in this system. In this measurement system the metal is always Pd, the results being applicable to other metals as noted below. Herein it is preferred for catalysts to contain bidentate ligands for which the second order rate constant for Ethylene Exchange Rate is about 20,000 L-molxe2x88x921sxe2x88x921 or less when the metal used in the polymerization catalyst is palladium, more preferably about 10,000 L-molxe2x88x921sxe2x88x921 or less, and more preferably about 5,000 L-molxe2x88x921sxe2x88x921 or less. When the metal in the polymerization catalyst is nickel, the second order rate constant (for the ligand in EER measurement) is about 50,000 L-molxe2x88x921sxe2x88x921, more preferably about 25,000 L-molxe2x88x921sxe2x88x921 or less, and especially preferably about 10,000 L-molxe2x88x921sxe2x88x921 or less. Herein the EER is measured using the compound (XI) in a procedure (including temperature) described in Examples 21-23. 
In these polymerizations it is preferred if the bidentate ligand is an xcex1-diimine. It is also preferred if the olefin has the formula R17CHxe2x95x90CH2, wherein R17 is hydrogen or n-alkyl.
In general for the polymers described herein, blends may be prepared with other polymers, and such other polymers may be elastomers, thermoplastics or thermosets. By elastomers are generally meant polymers whose Tg (glass transition temperature) and Tm (melting point), if present, are below ambient temperature, usually considered to be about 20xc2x0 C. Thermoplastics are those polymers whose Tg and/or Tm are at or above ambient temperature. Blends can be made by any of the common techniques known to the artisan, such as solution blending, or melt blending in a suitable apparatus such as a single or twin-screw extruder. Specific uses for the polymers of this application in the blends or as blends are listed below.
Blends may be made with almost any kind of elastomer, such as EP, EPDM, SBR, natural rubber, polyisoprene, polybutadiene, neoprene, butyl rubber, styrene-butadiene block copolymers, segmented polyester-polyether copolymers, elastomeric polyurethanes, chlorinated or chlorosulfonated polyethylene, (per)fluorinated elastomers such as copolymers of vinylidene fluoride, hexafluoropropylene and optionally tetrafluoroethylene, copolymers of tetrafluoroethylene and perfluoro(methyl vinyl ether), and copolymers of tetrafluoroethylene and propylene.
Suitable thermoplastics which are useful for blending with the polymers described herein include: polyesters such as poly(ethylene terephthalate), poly(butylene terephthalate), and poly(ethylene adipate); polyamides such as nylon-6, nylon-6,6, nylon-12, nylon-12,12, nylon-11, and a copolymer of hexamethylene diamine, adipic acid and terephthalic acid; fluorinated polymers such as copolymers of ethylene and vinylidene fluoride, copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of tetrafluoroethylene and a perfluoro(alkyl vinyl ether) such as perfluoro(propyl vinyl ether), and poly(vinyl fluoride); other halogenated polymers such a poly(vinyl chloride) and poly(vinylidene chloride) and its copolymers; polyolefins such as polyethylene, polypropylene and polystyrene, and copolymers thereof; (meth)acrylic polymers such a poly(methyl methacrylate) and copolymers thereof; copolymers of olefins such as ethylene with various (meth)acrylic monomers such as alkyl acrylates, (meth)acrylic acid and ionomers thereof, and glycidyl (meth)acrylate); aromatic polyesters such as the copolymer of Bisphenol A and terephthalic and/or isophthalic acid; and liquid crystalline polymers such as aromatic polyesters or aromatic poly(ester-amides).
Suitable thermosets for blending with the polymers described herein include epoxy resins, phenol-formaldehyde resins, melamine resins, and unsaturated polyester resins (sometimes called thermoset polyesters). Blending with thermoset polymers will often be done before the thermoset is crosslinked, using standard techniques.
The polymers described herein may also be blended with uncrosslinked polymers which are not usually considered thermoplastics for various reasons, for instance their viscosity is too high and/or their melting point is so high the polymer decomposes below the melting temperature. Such polymers include poly(tetrafluoroethylene), aramids such as poly(p-phenylene terephthalate) and poly(m-phenylene isophthalate), liquid crystalline polymer such as poly(benzoxazoles), and non-melt processible polyimides which are often aromatic polyimides.
All of the polymers disclosed herein may be mixed with various additives normally added to elastomers and thermoplastics [see EPSE (below), vol. 14, p. 327-410]. For instance reinforcing, non-reinforcing and conductive fillers, such as carbon black, glass fiber, minerals such as clay, mica and talc, glass spheres, barium sulfate, zinc oxide, carbon fiber, and aramid fiber or fibrids, may be used. Antioxidants, antiozonants, pigments, dyes, delusterants, compounds to promote crosslinking may be added. Plasticizers such as various hydrocarbon oils may also be used.
The following listing is of some uses for polyolefins, which are made from linear olefins and do not include polar monomers such as acrylates, which are disclosed herein. In some cases a reference is given which discusses such uses for polymers in general. All of these references are hereby included by reference. For the references, xe2x80x9cUxe2x80x9d refers to W. Gerhartz, et al., Ed., Ullmann""s Encyclopedia of Industrial Chemistry, 5th Ed. VCH Verlagsgesellschaft mBH, Weinheim, for which the volume and page number are given, xe2x80x9cECT3xe2x80x9d refers to the H. F. Mark, et al., Ed., Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., John Wiley and Sons, New York, xe2x80x9cECT4xe2x80x9d refers to the J. I Kroschwitz, et al., Ed., Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., John Wiley and Sons, New York, for which the volume and page number are given, xe2x80x9cEPSTxe2x80x9d refers to H. F. Mark, et al., Ed., Encyclopedia of Polymer Science and Technology, 1st Ed., John Wiley and Sons, New York, for which the volume and page number are given, xe2x80x9cEPSExe2x80x9d refers to H. F. Mark, et al., Ed., Encyclopedia of Polymer Science and Engineering, 2nd Ed., John Wiley and Sons, New York, for which volume and page numbers are given, and xe2x80x9cPMxe2x80x9d refers to J. A. Brydson, ed., Plastics Materials, 5 Ed., Butterworth-Heinemann, Oxford, UK, 1989, and the page is given. In these uses, a polyethylene, polypropylene and a copolymer of ethylene and propylene are preferred.
1. Tackifiers for low strength adhesives (U, vol. A1, p. 235-236) are a use for these polymers. Elastomeric and/or relatively low molecular weight polymers are preferred.
2. An oil additive for smoke suppression in single-stroke gasoline engines is another use. Elastomeric polymers are preferred.
3. The polymers are useful as base resins for hot melt adhesives (U, vol. A1, p. 233-234), pressure sensitive adhesives (U, vol. A1, p. 235-236) or solvent applied adhesives. Thermoplastics are preferred for hot melt adhesives. The polymers may also be used in a carpet installation adhesive.
4. Lubricating oil additives as Viscosity Index Improvers for multigrade engine oil (ECT3, Vol 14, p. 495-496) are another use. Branched polymers are preferred. Ethylene copolymer with acrylates or other polar monomers will also function as Viscosity Index Improvers for multigrade engine oil with the additional advantage of providing some dispersancy.5. Polymer for coatings and/or penetrants for the protection of various porous items such as lumber and masonry, particularly out-of-doors. The polymer may be in a suspension or emulsion, or may be dissolved in a solvent.
6. Base polymer for caulking of various kinds is another use. An elastomer is preferred. Lower molecular weight polymers are often used.
7. The polymers may be grafted with various compounds particularly those that result in functional groups such as epoxy, carboxylic anhydride (for instance as with a free radically polymerized reaction with maleic anhydride) or carboxylic acid (EPSE, vol. 12, p. 445). Such functionalized polymers are particularly useful as tougheners for various thermoplastics and thermosets when blended. When the polymers are elastomers, the functional groups which are grafted onto them may be used as curesites to crosslink the polymers. Maleic anhydride-grafted randomly-branched polyolefins are useful as tougheners for a wide range of materials (nylon, PPO, PPO/styrene alloys, PET, PBT, POM, etc.); as tie layers in multilayer constructs such as packaging barrier films; as hot melt, moisture-curable, and coextrudable adhesives; or as polymeric plasticizers. The maleic andhydride-grafted materials may be post reacted with, for example; amines, to form other functional materials. Reaction with aminopropyl trimethoxysilane would allow for moisture-curable materials. Reactions with di- and tri-amines would allow for viscosity modifications.
8. The polymers, particularly elastomers, may be used for modifying asphalt, to improve the physical properties of the asphalt and/or extend the life of asphalt paving.
9. The polymers may be used as base resins for chlorination or chlorosulfonation for making the corresponding chlorinated or chlorosulfonated elastomers. The unchlorinated polymers need not be elastomers themselves.
10. Wire insulation and jacketing may be made from any of the polyolefins (see EPSE, vol. 17, p. 828-842). In the case of elastomers it may be preferable to crosslink the polymer after the insulation or jacketing is formed, for example by free radicals.
11. The polymers, particularly the elastomers, may be used as tougheners for other polyolefins such as polypropylene and polyethylene.
12. The base for synthetic lubricants (motor oils) may be the highly branched polyolefins described herein (ECT3, vol. 14, p. 496-501).
13. The branched polyolefins herein can be used as drip suppressants when added to other polymers.
14. The branched polyolefins herein are especially useful in blown film applications because of their particular Theological properties (EPSE, vol. 7, p. 88-106). It is preferred that these polymers have some crystallinity.
15. The polymer described herein can be used to blend with wax for candles, where they would provide smoke suppression and/or drip control.
16. The polymers, especially the branched polymers, are useful as base resins for carpet backing, especially for automobile carpeting.
17. The polymers, especially those which are relatively flexible, are useful as capliner resins for carbonated and noncarbonated beverages.
18. The polymers, especially those having a relatively low melting point, are useful as thermal transfer imaging resins (for instance for imaging tee-shirts or signs).
19. The polymers may be used for extrusion or coextrusion coatings onto plastics, metals, textiles or paper webs.
20. The polymers may be used as a laminating adhesive for glass.
21. The polymers are useful as for blown or cast films or as sheet (see EPSE, vol. 7 p. 88-106; ECT4, vol. 11, p. 843-856; PM, p. 252 and p. 432ff). The films may be single layer or multilayer, the multilayer films may include other polymers, adhesives, etc. For packaging the films may be stretch-wrap, shrink-wrap or cling wrap. The films are useful form many applications such as packaging foods, geomembranes and pond liners. It is preferred that these polymers have some crystallinity.
22. The polymers may be used to form flexible or rigid foamed objects, such as cores for various sports items such as surf boards and liners for protective headgear. Structural foams may also be made. It is preferred that the polymers have some crystallinity. The polymer of the foams may be crosslinked.
23. In powdered form the polymers may be used to coat objects by using plasma, flame spray or fluidized bed techniques.
24. Extruded films may be formed from these polymers, and these films may be treated, for example drawn. Such extruded films are useful for packaging of various sorts.
25. The polymers, especially those that are elastomeric, may be used in various types of hoses, such as automotive heater hose.
26. The polymers, especially those that are branched, are useful as pour point depressants for fuels and oils.
27. These polymers may be flash spun to nonwoven fabrics, particularly if they are crystalline (see EPSE vol. 10, p. 202-253). They may also be used to form spunbonded polyolefins (EPSE, vol. 6, p. 756-760). These fabrics are suitable as house wrap and geotextiles.
28. The highly branched, low viscosity polyolefins would be good as base resins for master-batching of pigments, fillers, flame-retardants, and related additives for polyolefins.
29. The polymers may be grafted with a compound containing ethylenic unsaturation and a functional group such as a carboxyl group or a derivative of a carboxyl group, such as ester, carboxylic anhydride of carboxylate salt. A minimum grafting level of about 0.01 weight percent of grafting agent based on the weight of the grafted polymer is preferred. The grafted polymers are useful as compatibilizers and/or tougheners. Suitable grafting agents include maleic, acrylic, methacrylic, itaconic, crotonic, alpha-methyl crotonic and cinnamic acids, anhydrides, esters and their metal salts and fumaric acid and their esters, anhydrides (when appropriate) and metal salts.
Copolymers of linear olefins with 4-vinylcyclohexene and other dienes may generally be used for all of the applications for which the linear olefins polymers(listed above) may be used. In addition they may be sulfur cured, so they generally can be used for any use for which EPDM polymers are used, assuming the olefin/4-vinylcyclohexene polymer is elastomeric.
Also described herein are novel copolymers of linear olefins with various polar monomers such as acrylic acid and acrylic esters. Uses for these polymers are given below. Abbreviations for references describing these uses in general with polymers are the same as listed above for polymers made from linear olefins.
1. Tackifiers for low strength adhesives (U, vol. A1, p. 235-236) are a use for these polymers. Elastomeric and/or relatively low molecular weight polymers are preferred.
2. The polymers are useful as base resins for hot melt adhesives (U, vol. A1, p. 233-234), pressure sensitive adhesives (U, vol. A1, p. 235-236) or solvent applied adhesives. Thermoplastics are preferred for hot melt adhesives. The polymers may also be used in a carpet installation adhesive.
3. Base polymer for caulking of various kinds is another use. An elastomer is preferred. Lower molecular weight polymers are often used.
4. The polymers, particularly elastomers, may be used for modifying asphalt, to improve the physical properties of the asphalt and/or extend the life of asphalt paving, see U.S. Pat. No. 3,980,598.
5. Wire insulation and jacketing may be made from any of the polymers (see EPSE, vol. 17, p. 828-842). In the case of elastomers it may be preferable to crosslink the polymer after the insulation or jacketing is formed, for example by free radicals.
6. The polymers, especially the branched polymers, are useful as base resins for carpet backing, especially for automobile carpeting.
7. The polymers may be used for extrusion or coextrusion coatings onto plastics, metals, textiles or paper webs.
8. The polymers may be used as a laminating adhesive for glass.
9. The polymers are useful as for blown or cast films or as sheet (see EPSE, vol. 7 p. 88-106; ECT4, vol. 11, p. 843-856; PM, p. 252 and p. 432ff). The films may be single layer or multilayer, the multilayer films may include other polymers, adhesives, etc. For packaging the films may be stretch-wrap, shrink-wrap or cling wrap. The films are useful form many applications such as packaging foods, geomembranes and pond liners. It is preferred that these polymers have some crystallinity.
10. The polymers may be used to form flexible or rigid foamed objects, such as cores for various sports items such as surf boards and liners for protective headgear. Structural foams may also be made. It is preferred that the polymers have some crystallinity. The polymer of the foams may be crosslinked.
11. In powdered form the polymers may be used to coat objects by using plasma, flame spray or fluidized bed techniques.
12. Extruded films may be formed from these polymers, and these films may be treated, for example drawn. Such extruded films are useful for packaging of various sorts.
13. The polymers, especially those that are elastomeric, may be used in various types of hoses, such as automotive heater hose.
14. The polymers may be used as reactive diluents in automotive finishes, and for this purpose it is preferred that they have a relatively low molecular weight and/or have some crystallinity.
15. The polymers can be converted to ionomers, which when the possess crystallinity can be used as molding resins. Exemplary uses for these ionomeric molding resins are golf ball covers, perfume caps, sporting goods, film packaging applications, as tougheners in other polymers, and usually extruded) detonator cords.
16. The functional groups on the polymers can be used to initiate the polymerization of other types of monomers or to copolymerize with other types of monomers. If the polymers are elastomeric, they can act as toughening agents.
17. The polymers can act as compatibilizing agents between various other polymers.
18. The polymers can act as tougheners for various other polymers, such as thermoplastics and thermosets, particularly if the olefin/polar monomer polymers are elastomeric.
19. The polymers may act as internal plasticizers for other polymers in blends. A polymer which may be plasticized is poly(vinyl chloride).
20. The polymers can serve as adhesives between other polymers.
21. With the appropriate functional groups, the polymers may serve as curing agents for other polymers with complimentary functional groups (i.e., the functional groups of the two polymers react with each other).
22. The polymers, especially those that are branched, are useful as pour point depressants for fuels and oils.
23. Lubricating oil additives as Viscosity Index Improvers for multigrade engine oil (ECT3, Vol 14, p. 495-496) are another use. Branched polymers are preferred. Ethylene copolymer with acrylates or other polar monomers will also function as Viscosity Index Improvers for multigrade engine oil with the additional advantage of providing some dispersancy.
24. The polymers may be used for roofing membranes.
25. The polymers may be used as additives to various molding resins such as the so-called thermoplastic olefins to improve paint adhesion, as in automotive uses.
Polymers with or without polar monomers present are useful in the following uses. Preferred polymers with or without polar monomers are those listed above in the uses for each xe2x80x9ctypexe2x80x9d.
1. A flexible pouch made from a single layer or multilayer film (as described above) which may be used for packaging various liquid products such as milk, or powder such as hot chocolate mix. The pouch may be heat sealed. It may also have a barrier layer, such as a metal foil layer.
2. A wrap packaging film having differential cling is provided by a film laminate, comprising at least two layers; an outer reverse which is a polymer (or a blend thereof) described herein, which contains a tackifier in sufficent amount to impart cling properties; and an outer obverse which has a density of at least about 0.916 g/mL which has little or no cling, provided that a density of the outer reverse layer is at least 0.008 g/mL less than that of the density of the outer obverse layer. It is preferred that the outer obverse layer is linear low density polyethylene, and the polymer of the outer obverse layer have a density of less than 0.90 g/mL. All densities are measured at 25xc2x0 C.
3. Fine denier fibers and/or multifilaments. These may be melt spun. They may be in the form of a filament bundle, a non-woven web, a woven fabric, a knitted fabric or staple fiber.
4. A composition comprising a mixture of the polymers herein and an antifogging agent. This composition is especially useful in film or sheet form because of its antifogging properties.
5. Elastic, randomly-branched olefin polymers are disclosed which have very good processability, including processing indices (PI""s) less than or equal to 70 percent of those of a comparative linear olefin polymer and a critical shear rate at onset of surface melt fracture of at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a traditional linear olefin polymer at about the same I2 Mw/Mn. The novel polymers may have higher low/zero shear viscosity and lower high shear viscosity than comparative linear olefin polymers made by other means. These polymers may be characterized as having: a) a melt flow ratio, I10/I2,xe2x89xa75.63, b) a molecular weight distribution, Mw/Mn, defined by the equation: Mw/Mnxe2x89xa7 (I10/I2)xe2x88x924.63, and c) a critical shear rate at onset of surface melt fracture of at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear olefin polymer having about the same I2 and Mw/Mn. Some blends of these polymer are characterized as having: a) a melt flow ratio, I10/I2,xe2x89xa75.63, b) a molecular weight distribution, Mw/Mn, defined by the equation: Mw/Mnxe2x89xa7 (I10/I2)xe2x88x924.63, and c) a critical shear rate at onset of surface melt fracture of at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear olefin polymer having about the same I2 and Mw/Mn and (b) at least one other natural or synthetic polymer chosen from:
(a) a polyolefin, which contains about 80 to about 150 branches per 1000 methylene groups, and which contains for every 100 branches that are methyl, about 30 to about 90 ethyl branches, about 4 to about 20 propyl branches, about 15 to about 50 butyl branches, about 3 to about 15 amyl branches, and about 30 to about 140 hexyl or longer branches.
(b) the polyolefin as recited in (a), which is an ethylene homopolymer;
(c) a polyolefin which contains about 20 to about 150 branches per 1000 methylene groups, and which contains for every 100 branches that are methyl, about 4 to about 20 ethyl branches, about 1 to about 12 propyl branches, about 1 to about 12 butyl branches, about 1 to about 10 amyl branches, and 0 to about 20 hexyl or longer branches.
(d) the polyolefin as recited in (c), which is an ethylene homopolymer;
(e) an ethylene homopolymer with a density of 0.86 g/ml or less;
(f) a homopolypropylene with a glass transition temperature of xe2x88x9230xc2x0C. or less, provided that said homopolypropylene has at least 50 branches per 1000 methylene groups;
(g) a conventional high density polyethylene;
(h) low density polyethylene; or
(i) linear low density polyethylene polymer.
The polymers may be further characterized as having a melt flow ratio, I10/I2,xe2x89xa75.63, a molecular weight distribution, Mw/Mn, defined by the equation; Mw/Mnxe2x89xa7 (I10/I2)xe2x88x924.63, and a critical shear stress at onset of gross melt fracture of greater than about 400 kPa (4xc3x97106 dyne/cm2) and their method of manufacture are disclosed. The randomly-branched olefin polymers preferably have a molecular weight distribution from about 1.5 to about 2.5. The polymers described herein often have improved processability over conventional olefin polymers and are useful in producing fabricated articles such as fibers, films, and molded parts. For this paragraph, the value is I2 is measured in accordance with ASTM D-1238-190/2. 16 and I10 is measured in accordance with ASTM D-1238-190/10; critical shear rate at least onset of surface which is hereby included by reference.
In another process described herein, the product of the process described herein is a xcex1-olefin. It is preferred that in the process a linear xcex1-olefin is produced. It is also preferred that the xcex1-olefin contain 4 to 32, preferably 8 to 20, carbon atoms. 
When (XXXI) is used as a catalyst, a neutral Lewis acid or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion is also present as part of the catalyst system (sometimes called a xe2x80x9cfirst compoundxe2x80x9d in the claims). By a xe2x80x9cneutral Lewis acidxe2x80x9d is meant a compound which is a Lewis acid capable for abstracting Xxe2x88x92 from (I) to form a weakly coordinating anion. The neutral Lewis acid is originally uncharged (i.e., not ionic). suitable neutral Lewis acids include SbF5, Ar3B (wherein Ar is aryl), and BF3. By a cationic Lewis acid is meant a cation with a positive charge such as Ag+, H+, and Na+.
A preferred neutral Lewis acid is an alkyl aluminum compound, such as R93Al, R92AlCl, R9AlCl2, and xe2x80x9cR9AlOxe2x80x9d (alkylaluminoxane), wherein R9 is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4 carbon atoms. Suitable alkyl aluminum compounds include methylaluminoxane, (C2H5)2AlCl, C2H5AlCl2, and [(CH3)2CHCH2]3Al.
Relatively noncoordinating anions are known in the art, and the coordinating ability of such anions is known and has been discussed in the literature, see for instance W. Beck., et al., Chem. Rev., vol. 88 p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p. 927-942 (1993), both of which are hereby included by reference. Among such anions are those formed from the aluminum compounds in the immediately preceding paragraph and Xxe2x88x92, including R93AlXxe2x88x92, R92AlClXxe2x88x92, R9AlCl2Xxe2x88x92, and xe2x80x9cR9AlOXxe2x88x92xe2x80x9d. Other useful noncoordinating anions include BAFxe2x88x92{BAF=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate}, SbF6xe2x88x92, PF6xe2x88x92, and BF4xe2x88x92, trifluoromethanesulfonate, p-toluenesulfonate, (RfSO2)2Nxe2x88x92, and (C6F5)4Bxe2x88x92.
The temperature at which the process is carried out is about xe2x88x92100xc2x0 C. to about +200xc2x0 C., preferably about 0xc2x0 C. to about 150xc2x0 C., more preferably about 25xc2x0 C. to about 100xc2x0 C. It is believed that at higher temperatures, lower molecular weight xcex1-olefins are produced, all other factors being equal. The pressure at which the polymerization is carried out is not critical, atmospheric pressure to about 275 MPa being a suitable range. It is also believed that increasing the pressure increases the relative amount of xcex1-olefin (as opposed to internal olefin) produced.
The process to make xcex1-olefins may be run in a solvent (liquid), and that is preferred. The solvent may in fact be the xcex1-olefin produced. Such a process may be started by using a deliberately added solvent which is gradually displaced as the reaction proceeds. By solvent it is not necessarily meant that any or all of the starting materials and/or products are soluble in the (liquid) solvent.
In (I) it is preferred that R3 and R4 are both hydrogen or methyl or R3 and R4 taken together are 
It is also preferred that each of Q and S is independently chlorine or bromine, and it is more preferred that both of Q and S in (XXXI) are chlorine or bromine.
In (XXXI) R2 and R5 are hydrocarbyl or substituted hydrocarbyl. What these groups are greatly determines whether the xcex1-olefins of this process are made, or whether higher polymeric materials, i.e., materials containing over 25 ethylene units, are coproduced or produced almost exclusively. If R2 and R5 are highly sterically hindered about the nickel atom, the tendency is to produce higher polymeric material. For instance, when R2 and R5 are both 2,6-diisopropylphenyl mostly higher polymeric material is produced. However, when R2 and R5 are both phenyl, mostly the xcex1-olefins of this process are produced. of course this will also be influenced by other reaction conditions such as temperature and pressure, as noted above. Useful groups for R2 and R5 are phenyl, and p-methylphenyl.
As is understood by the artisan, in oligomerization reactions of ethylene to produce xcex1-olefins, usually a mixture of such xcex1-olefins is obtained containing a series of such xcex1-olefins differing from one another by two carbon atoms (an ethylene unit. The process for preparing xcex1-olefins described herein produces products with a high percentage of terminal olefinic groups (as opposed to internal olefinic groups). The product mixture also contains a relatively high percentage of molecules which are linear. Finally relatively high catalyst efficiencies can be obtained.
The xcex1-olefins described as being made herein may also be made by contacting ethylene with one of the compounds 
wherein R2, R3, R4, and R5 are as defined (and preferred) as described above (for the preparation of xcex1-olefins), and T1 is hydrogen or n-alkyl containing up to 38 carbon atoms, Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6, U is n-alkyl containing up to 38 carbon atoms, and X is a noncoordinating anion (see above). The process conditions for making xcex1-olefins using (III) or (XXXIV) are the same as for using (XXXI) to make these compounds except a Lewis or Bronsted acid need not be present. Note that the double line in (XXXIV) represents a coordinated ethylene molecule. (XXXIV) may be made from (II) by reaction of (III) with ethylene. In other words, (XXXIV) may be considered an active intermediate in the formation of xcex1-olefin from (III). Suitable groups for Z include dialkyl ethers such as diethyl ether, and alkyl nitrites such as acetonitrile.
In general, xcex1-olefins can be made by this process using as a catalyst a Ni[II] complex of an xcex1-diimine of formula (VIII), wherein the NI[II] complex is made by any of the methods which are described above, using Ni[0], Ni[I] or Ni[II] precursors. All of the process conditions, and preferred groups on (VIII), are the same as described above in the process for making xcex1-olefins.